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Heinemann

CHEMISTRY 5TH EDITION

VCE Units 3 & 4


Written for the VCE Chemistry
Study Design 2017 –2021

Chris Commons Lanna Derry Maria Porter Robert Sanders Elizabeth Freer
Penny Commons Bob Hogendoorn Geoff Quinton Drew Chan Simon Gooding
Elissa Huddart Bob Ross Erin Bruns
Pat O’Shea Patrick Sanders Vicky Ellis
Heinemann

CHEMISTRY 5TH EDITION

VCE Units 3 & 4


COORDINATING AUTHORS
Chris Commons
Penny Commons
AUTHORS
Lanna Derry
Bob Hogendoorn
Elissa Huddart
Pat O’Shea
Maria Porter
Geoff Quinton
Bob Ross
Patrick Sanders
Robert Sanders

CONTRIBUTING AUTHORS
Drew Chan
Erin Bruns
Vicky Ellis
Elizabeth Freer
Simon Gooding
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Heinemann Chemistry 2 5e
Series Consultant: Malcolm Parsons
Project Lead: Caroline Williams
Project Managers: Hannah Turner, Susan Keogh and Shelly Wang
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Creator: Commons, C, author.
Title: Heinemann chemistry 2 / Chris Commons [and sixteen others]
Edition: 5th edition
ISBN: 9781488611254 (paperback)
Notes: Includes index.
Previous edition: 2010.
Target Audience: For year 12 students.
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Heinemann

CHEMISTRY 5TH EDITION

Writing and Development Team


We are grateful to the following people for their time and expertise in contributing to the
Heinemann Chemistry 2 project.

Malcolm Parsons John Gilson Bob Ross


Publishing Consultant Educator Teacher
Series Consultant Reviewer Author

Chris Commons Simon Gooding Patrick Sanders


Teacher Teacher Teacher
Coordinating Author Contributing Author Author

Penny Commons Bob Hogendoorn Robert Sanders


Lecturer Senior Consultant Education Consultant
Coordinating Author Author Author

Drew Chan Elissa Huddart


Teacher Teacher
Subject Lead (Print) Author The Chemistry Education
Contributing Author Association was formed
Louise Lennard in 1977 by a group of
Erin Bruns Teacher chemistry teachers from
Teacher Contributor secondary and tertiary institutions.
Subject Lead (Print) It aims to promote the teaching of
Pat O’Shea chemistry, particularly in secondary
Contributing Author
Teacher schools. The CEA has established
Donna Chapman Author a tradition of providing up-to-date
text and electronic material and
Laboratory Technician
Neale Peters support resources for both students
Contributor
Teacher and teachers and professional
development opportunities for
Lanna Derry Contributor
teachers.
Teacher
Author Maria Porter The CEA offers scholarships
Teacher and bursaries to students and
Vicky Ellis Author teachers to further their interest in
Teacher chemistry. The CEA supports STAV
Contributing Author Geoff Quinton with sponsorship for the Chemistry
Teacher Conference, Science Drama Awards
Elizabeth Freer Author and The Science Talent Search.
Teacher
Contributing Author
Unit 3: How can chemical processes be designed
to optimise efficiency?
AREA OF STUDY 1 AREA OF STUDY 2
What are the options for energy How can the yield of a chemical product
production? be optimised?
Chapter 1 Fuels 1 Chapter 7 Rate of chemical reactions 169
1.1 Types of fuels 2 7.1 Investigating the rate of chemical
1.2 Fossil fuels and biofuels 11 reactions 170
1.3 Petrodiesel and biodiesel 24 7.2 Collision theory 175
Chapter 1 review 33 7.3 Effect of temperature on rate of reaction 179
7.4 Catalysts 184
Chapter 2 Energy from fuels 35
Chapter 7 review 189
2.1 Exothermic and endothermic reactions 36
2.2 Thermochemical equations and energy Chapter 8 Extent of chemical reactions 193
profile diagrams 40 8.1 Dynamic equilibrium 194
2.3 Energy from combustion 46 8.2 The equilibrium law 203
2.4 Determining the heat of combustion 8.3 Working with equilibrium constants 208
of fuels 54 8.4 Calculations involving equilibrium 211
Chapter 2 review 61 8.5 Le Châtelier’s principle 216
Chapter 3 Stoichiometry and the combustion 8.6 Further applications of Le Châtelier’s
of fuels 63 principle 222
3.1 Introducing gases 64 8.7 Optimising the yield of industrial
3.2 Universal gas equation 72 processes 230
3.3 Calculations involving combustion Chapter 8 review 235
of fuels—Part 1 81 Chapter 9 Production of chemicals
3.4 Calculations involving combustion by electrolysis 239
of fuels—Part 2 85 9.1 Electrolytic cells 240
3.5 Calculations involving energy changes 91 9.2 Commercial electrolytic cells 246
Chapter 3 review 98 9.3 Faraday’s laws 252
Chapter 4 Redox reactions 101 Chapter 9 review 258
4.1 Oxidation and reduction 102 Area of Study 2—Review 261
4.2 Oxidation numbers 107
4.3 Writing complex redox equations 115
Chapter 4 review 122
Chapter 5 Galvanic cells as a source of energy 125
5.1 Galvanic cells 126
5.2 The electrochemical series 133
5.3 Predicting direct redox reactions 139
5.4 Everyday sources of power 142
Chapter 5 review 148
Chapter 6 Fuel cells as a source of energy 151
6.1 Continuous sources of electrical energy 152
Chapter 6 review 161
Area of Study 1—Review 163
Unit 4: How are organic compounds categorised,
analysed and used?
AREA OF STUDY 1 14.3 Redox titrations of organic compounds 444
How can the diversity of carbon Chapter 14 review 450
compounds be explained and categorised? Area of Study 1—Review 453
Chapter 10 Structure and nomenclature of
organic compounds 271 AREA OF STUDY 2
10.1 Diversity of carbon compounds 272 What is the chemistry of food?
10.2 Stereoisomers 281 Chapter 15 Structure and bonding in food
10.3 Hydrocarbons 289 molecules 461
10.4 Functional groups—Part 1 297 15.1 Amino acids 462
10.5 Functional groups—Part 2 304 15.2 The formation of proteins 468
10.6 An overview of IUPAC nomenclature 310 15.3 Primary and secondary structures
Chapter 10 review 316 of proteins 474
15.4 Tertiary and quaternary structures
Chapter 11 Properties and reactions of
organic compounds 319 of proteins 480
11.1 Boiling points and solubilities of organic 15.5 Fats and oils 486
compounds 320 15.6 Carbohydrates 495
11.2 Viscosities and flashpoints of organic 15.7 Vitamins 505
compounds 330 Chapter 15 review 511
11.3 Chemical properties of alkanes, Chapter 16 Metabolism of food in the
haloalkanes and alkenes 336 human body 515
11.4 Reactions of alcohols, carboxylic acids 16.1 Metabolism of food 516
and esters 345 16.2 Action of enzymes 527
11.5 Reaction pathways 354 16.3 Enzymes—dependence on pH and
11.6 Yield and the chemical industry 361 temperature 536
Chapter 11 review 366 16.4 Hydrolysis of carbohydrates 544
16.5 Hydrolysis of fats and oils 551
Chapter 12 Analysis of organic compounds
Chapter 16 review 562
by spectroscopic techniques 369
12.1 Infrared spectroscopy 370 Chapter 17 The energy content of food 565
12.2 Nuclear magnetic resonance spectroscopy 381 17.1 Food—an energy source 566
12.3 Mass spectrometry 393 17.2 Introducing calorimetry 572
12.4 Determination of molecular structure 17.3 Calibration of calorimeters 580
by spectroscopy 400 Chapter 17 review 589
Chapter 12 review 410 Area of Study 2—Review 593
Chapter 13 Analysis of organic compounds
Area of Study 3—Practical Investigation
by chromatography 413
at Heinemann Chemistry 2 5th Edition ProductLink
13.1 Principles of chromatography 414
13.2 High-performance liquid chromatography 418 APPENDICES 599
Chapter 13 review 426 ANSWERS 602
Chapter 14 Analysis of organic compounds GLOSSARY 640
by volumetric analysis 429 INDEX 648
14.1 Principles of volumetric analysis 430 ACKNOWLEDGEMENTS 657
14.2 Acid–base titrations of organic compounds 436 PERIODIC TABLE 662
How to use this book
Heinemann Chemistry 2
5th edition
Heinemann Chemistry 2 5th Edition has
been written to the new VCE Chemistry Chapter opener
Study Design 2017–2021. The book covers Chapter opening
Units 3 and 4 in an easy-to-use resource. pages link the
Explore how to use this book below. Study Design to the
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vi
Glossary Chapter review
Key terms are shown in bold and Each chapter concludes
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vii
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viii
UNIT
How can chemical
processes be designed
to optimise efficiency?
AREA OF STUDY 1

What are the options for energy production?


Outcome 1: On completion of this unit the student should be able to compare fuels
quantitatively with reference to combustion products and energy outputs, apply
knowledge of the electrochemical series to design, construct and test galvanic cells,
and evaluate energy resources based on energy efficiency, renewability and
environmental impact.

AREA OF STUDY 2

How can the yield of a chemical product be optimised?


Outcome 2: On completion of this unit the student should be able to apply rate and
equilibrium principles to predict how the rate and extent of reactions can be optimised,
and explain how electrolysis is involved in the production of chemicals and in the
recharging of batteries.

VCE Biology Study Design extracts © VCAA (2015); reproduced by permission.

ix
CHAPTER

Fuels

In this chapter, you will learn how fuels are used to meet global energy needs
and you will gain an appreciation of the chemistry that underpins decisions about
the use of fuels. Combustion reactions are used to release useful heat energy
from the chemical energy stored in fuels. You will explore how fuels vary in terms
of the energy that they produce when they are burnt.
You will consider the environmental impact of using different types of fuels,
including their carbon emissions as well as the other pollutants they release
into the atmosphere. Current research being conducted into the production of
renewable fuels and the potential for reducing the harmful impact of fossil fuels
will also be discussed.

Key knowledge
• The definition of a fuel, including the distinction between fossil fuels and
biofuels with reference to origin and renewability (ability of a resource to
be replaced by natural processes within a relatively short period of time)
• Combustion of fuels as exothermic reactions with reference to the use of the
joule as the SI unit of energy, energy transformations and their efficiencies
• The comparison of fossil fuels (coal, crude oil, petroleum gas, coal seam gas)
and biofuels (biogas, bioethanol, biodiesel) with reference to energy content,
renewability and environmental impacts related to sourcing and combustion
• The comparison of the suitability of petrodiesel and biodiesel as transport
fuels with reference to sources, chemical structures, combustion products, flow
along fuel lines (implications of hygroscopic properties and impact of outside
temperature on viscosity) and the environmental impacts associated with their
extraction and production

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


1.1 Types of fuels
Fuels provide you with energy. They are substances that have chemical energy
stored within them. All chemicals contain stored energy. What makes a fuel special
is that this stored chemical energy can be released relatively easily.
Sugar is an example of a common fuel (Figure 1.1.1). A cube of table sugar
(sucrose) can provide your body with 82 kilojoules of energy. This is about 1%
of your daily energy needs. If sucrose is burnt, this energy is released as heat. The
combustion of 1 kilogram of sucrose releases sufficient energy to melt more than
5 kilograms of ice and then boil all the liquid water produced.
Although sugars provide energy for your body, you do not heat your home,
power cars or produce electricity by burning sugar. A range of other fuels such as
wood, coal, oil, natural gas, LPG, ethanol and petrol (Figure 1.1.2) are used for
FIGURE 1.1.1 Sugars, such as sucrose, are fuels these energy needs.
In this section, you will explore the range of fuels available and how they
are sourced.

THE NEED FOR FUELS


A fuel is a substance with stored energy that can be released relatively easily for
use as heat or power. Although this chapter will focus on fuels with stored chemical
energy, the term ‘fuel’ is also applied to sources of nuclear energy, such as uranium.
The use of fuels by society can be considered from a number of points of view,
including at a:
• local level (e.g. the type of petrol used in your car)
• national level (e.g. whether Australia’s use of energy resources is sustainable)
• global level (e.g. whether the use of fossil fuels (coal, oil and natural gas) is
FIGURE 1.1.2 Petrol is just one type of fuel that contributing to the enhanced greenhouse effect).
These are not separate issues. Choices made locally have regional and global
effects. The decisions of global and national governments affect how and which
fuels are used.

Units of energy
The international system of units (SI units) is a widely used system of measurement
that specifies units for a range of quantities. The SI unit for energy is the joule,
symbol J. As 1 J of energy is a relatively small amount, it is common to see the
following units in use:
• kilojoules, 1 kJ = 103 J
transportation • megajoules, 1 MJ = 106 J
(47%)
• gigajoules, 1 GJ = 109 J
• terajoules, 1 TJ = 1012 J.

heating
(40%)
World energy consumption is around 4 × 1020 joules per year. The United States
consumes a quarter of the world’s energy. Australia consumes about one-hundredth
of the world’s energy. But energy consumption per person in Australia is only just
cooking below that of the United States. Figure 1.1.3 shows the ways in which Australians
(2%)
lighting use energy. As you can see, heating and transportation account for 87% of Australia’s
and motors other—including total energy consumption.
(7%) refrigeration, electrolysis In Australia and around the world, most of the energy used for heating,
(4%)
electricity generation and powering vehicles comes from fossil fuels. About 86% of
FIGURE 1.1.3 This pie chart shows where Australian electricity is generated from these fuels, with 73% from coal and 13% from
natural gas.

2 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Coal-fired power stations are the dominant source of the world’s electricity
because they are often the cheapest form of generation. Electricity from coal-fired
power stations is reliable and coal is very abundant.
About 14% of Australia’s electricity comes from renewable energy sources.
Hydroelectricity contributes 7% of total electricity and wind, biofuels and solar
energy make up the other 7%.

Future energy needs


Burning wood was the dominant method of obtaining energy up to the middle of
the 19th century. Wood supplies once seemed unlimited and, like fossil fuels today,
satisfied most of the demands of the time.
Fossil fuels now provide nearly 90% of the world’s energy needs. As members of
a society that is heavily dependent on fossil fuels as a source of energy, we can find
it hard to imagine obtaining energy from elsewhere.
The world first became aware that fossil fuels are a finite energy reserve during
the ‘oil crisis’ of the early 1970s. Several Middle Eastern oil exporters restricted
production for political reasons. This dramatically increased the cost of crude oil
and caused huge increases in the price of petrol around the world.
Given the limited reserves and concerns about the link between fossil fuels
and climate change, there is considerable interest in identifying and developing
new energy sources. Many countries are already considering alternative sources of
energy. The development of alternative sources for large-scale energy production is
not a simple task. Replacement energy sources need to meet a range of requirements,
such as being reliable, sustainable and cost-effective. Figure 1.1.4 shows the increase
in world energy production from different sources.

600 new technologies


nuclear
500 hydroelectricity
Energy (1018 joules)

400 natural gas

300 oil

200
coal
100
biofuels
0
1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020
Year
FIGURE 1.1.4

FOSSIL FUELS
Non-renewable resources are those that are used faster than they can be replaced.
Coal, oil and natural gas are non-renewable fuels. Reserves of fossil fuels are limited
and they could eventually be exhausted.

Formation of fossil fuels


Coal, oil and natural gas were formed from ancient plants, animals and
microorganisms. Buried under tonnes of mud, sand and rock, this once biological
material has undergone complex changes to become the fossil fuels used by
societies today. The organic matter still retains some of the chemical energy the
plants originally accumulated by carrying out photosynthesis. Chemical energy
in fossil fuels can be considered to be trapped solar energy.
Fossil fuel formation occurs over millions of years. This is why these fuels are
considered non-renewable. Once reserves of the fossil fuels have been used, they
will not be replaced in the foreseeable future.

CHAPTER 1 | FUELS 3
Coal
As wood and other plant material turn into coal, gradual chemical changes occur.
Wood is about 50% carbon. As wood is converted into coal, the carbon content
increases and the proportion of hydrogen and oxygen decreases. The wood
Decaying
vegetation progressively becomes peat, brown coal and then black coal (see Figure 1.1.5).
Coal is a mixture of large molecules made from carbon, hydrogen, nitrogen, sulfur
and other elements.
Peat

Increasing time, pressure, temperature


60% carbon The amount of water in coal decreases as these changes occur. When coal is
Heat released 25 kJ g–1 burnt, the energy released causes the water to vaporise, reducing the net amount of
Increasing quality as fuel

heat released. Black coal, which contains the least water and therefore the highest
percentage of carbon, is a better fuel than brown coal or peat.
Although black coal is usually buried further underground than brown coal,
Brown coal
70% carbon its higher heat value often makes it economical to mine. Black coal is mined in
Heat released 30 kJ g–1 Queensland and New South Wales. It is used for domestic power generation or
exported overseas.
Large brown coal deposits are located in the Latrobe Valley in Victoria (see
Black coal Figure 1.1.6). The power stations located next to these open-cut mines burn brown
90% carbon coal to generate electricity. Australia is the fifth largest producer of coal and the
Heat released 35 kJ g–1 second largest exporter of coal in the world.

FIGURE 1.1.5

FIGURE 1.1.6

CHEMFILE crude oil, drilling into the impermeable rock has to take place (see
Forming crude oil pressure that has gradually built up from when the oil was formed.
The main deposits of crude oil were formed from small
marine animals (zooplankton) and plants (phytoplankton)
that lived up to 1 billion years ago. Some crude oil deposits
are estimated to be even older, as much as 3–4 billion years

19th century in the United States. Today, the largest crude oil
deposits are in Russia, Iran, Iraq and Saudi Arabia. New crude oil
deposits are still being found throughout the world. The oldest
deposits found so far are in Venezuela, where the oil is estimated
to be almost 4 billion years old. However, only about 10% of the

Permeable rocks contain tiny spaces through which liquid


substances can move. Crude oil has a lower density than water,
so oil migrates upwards through permeable rocks over time.
Large deposits of oil are formed when portions of this migrating
FIGURE 1.1.7

4 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Fuels from crude oil
Crude oil (petroleum) is a mixture of hydrocarbon molecules that are mostly
members of the homologous series of alkanes. Crude oil itself is of no use as a
fuel, but it contains many useful compounds.
Crude oil is separated into a range of fractions by fractional distillation.
Fractional distillation does not produce pure substances. Each fraction is still a
mixture of hydrocarbon compounds. These fractions can be used as fuels, or treated Alkanes are hydrocarbons with
further to produce more specific products through chemical processes. the general formula CnH2n+2.
The relative amounts of different alkanes in crude oil vary with the deposit. For Alkanes are commonly found
example, oil from Bass Strait and the Carnarvon Basin, Western Australia, contains
relatively few of the larger molecules needed to form lubricants and bitumen.

CHEMISTRY IN ACTION

Fractional distillation of crude oil emand


in oil for product
(C1–C4) for chemical

bubble cap 100°C


(C5–C7)
250°C
(C8–C12)
325°C
(C10–C18)
crude oil 375°C
(C12–C20) petrol
petrol

400°C
heater

fractionating column
(>C20)

FIGURE 1.1.8

Fractional distillation uses heat to separate a mixture into a The boiling point of a molecular compound depends
number of different parts or fractions. A number of different on the strength of its intermolecular forces. Attractions
temperatures are produced because of the nature of the between non-polar alkane molecules arise from weak
column in which the crude oil is placed. The temperature dispersion forces, which are stronger with increasing
of the tower decreases gradually with increasing height. molecular mass. As a result, each fraction consists of
Within the tower are horizontal trays, each containing alkanes within a specific mass range. Lighter alkanes
hundreds of bubble caps. Bubble caps impede (stop) condense near the top of the tower, whereas heavier
the upwards movement of gases (see Figure 1.1.8). As alkanes condense near the bottom. The composition
the vapour rises, it forces the caps up and it bubbles and boiling range of each fraction are summarised in
through condensed liquid in the trays. Those substances Figure 1.1.8. For example, the petrol fraction that boils
in the vapour that have boiling points almost equal to the (and condenses) between 100°C and 250°C consists
temperature of the liquid in the trays condense and are of alkanes containing 8–12 carbon atoms; that is, C8H18
collected. Consequently, fractions collected from trays to C12H26.
higher in the tower will have lower boiling points.

Oil reserves
Australia’s relatively small oil reserves are likely to be exhausted later this century.
Figure 1.1.9 (page 6) shows the current locations of Australian oil, gas and coal
fields. These reserves are associated with giant offshore gas fields near the northern
Western Australian coast, and in reserves in outback South Australia and Bass
Strait. Australia already imports over 90% of the crude oil it uses. Importation of
large amounts of oil has a significant impact on Australia’s economy.
CHAPTER 1 | FUELS 5
Bonaparte Basin
18.6% DARWIN

16.9%
Browse Basin Laura Basin
16.0%

18.3%

Galilee
Carnarvon Basin Basin

49.7% Bowen Basin

55.7% Amadeus Basin


0.1%
Cooper/Eromanga
Surat Callide Basin
0.1% Basin
Basin Maryborough
Adavalle Basin Basin
Arekaringa
Tarong Basin
Basin Bowen/Surat Moreton Basin
Basin BRISBANE
Perth Basin
Perth Basin Leigh Creek Gunnedah Basin
0.8% PERTH
Gloucester Basin
0.6%
Sydney Basin
Collie SYDNEY
ADELAIDE WOLLONGONG
Oaklands Basin
PORT KEMBLA
Bacchus Latrobe
Oil and gas basins Oil basin: producing Marsh Valley
Resources are shown as a percentage Anglesea
of total resources. Estimated Australian MELBOURNE Gippsland Basin
Oil basin: not producing Bass 10.9%
resources as at 1 January 2003 Otway Basin
Gas = 167 285 PJ Basin 5.1%
Liquids = 32 601 PJ Gas basin: producing 0.2%
(Geoscience Australia 2004) 1.89% Fingal
1.0%
Coal basins Gas basin: not producing HOBART
0.4%
Uranium mineral deposit Coal basin: producing

FIGURE 1.1.9

Natural gas
Natural gas is another fossil fuel found in deposits in the Earth’s crust. It is mainly
composed of methane (CH4) together with small amounts of other hydrocarbons
such as ethane (C2H6) and propane (C3H8). Water, sulfur, carbon dioxide and
well nitrogen may also be present in natural gas.
Natural gas can be found:
• in gas reservoirs trapped between layers of rocks
• as a component of petroleum deposits
• in coal deposits where it is bonded to the surface of the coal. Coal seams usually
contain water and the pressure of the water can keep the gas adsorbed to the
coal surface. Natural gas found this way is known as coal seam gas or CSG.
It is a major component of the energy supplies of Queensland
FIGURE 1.1.10 • trapped in shale rock, where it is referred to as shale gas. Shale gas is mined in
many parts of the United States.
Natural gas is accessed by drilling as with crude oil; drilling causes the natural
gas to flow to the surface (see Figure 1.1.10).

6 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Fracking
The extraction of natural gas from coal or shale deposits usually involves a process
called fracking. Under pressure, the natural gas is adsorbed on the surface of the
coal or shale. Fracking is used to fracture the rock or coal to release the natural gas.
Fracking begins with drilling a well into the deposit to access the trapped gas.
The well is encased in steel and concrete to prevent leakage into local water supplies.
Fracking fluid is then pumped down the well at extremely high pressures. This
high-pressure fluid fractures the surrounding rock or coal, creating fissures through
which gas can flow. This process is shown in Figure 1.1.11.
Materials used for fracking include sand, water and other chemicals. There are
concerns about the potential impact of this process on the local environment and
underground water supplies.

well
w

FIGURE 1.1.11

CHEMISTRY IN ACTION

Debate surrounding coal seam gas


Coal seam gas (CSG) is a natural gas that is extracted from underground coal
seams, where it is trapped in pores in the coal. Almost 30% of Australia’s natural
gas reserves come from coal seam gas. Reserves of CSG are found in New South
Wales and Queensland. It is predicted that the reserves of CSG could supply the
eastern states of Australia for over 25 years.
Various chemicals have been used as fracking fluids. Fracking fluids increase
the permeability of the rock and therefore flow of gas to the surface. Fluids such
as benzene, toluene, xylene and ethylbenzene were once commonly used. The
use of these fluids has been banned in both New South Wales and Queensland
because of concern over their effect on the environment. For example, these
potentially carcinogenic compounds may escape and contaminate groundwater.
Water is now commonly used as a fracking fluid. Generally, large amounts of
water are not available at the fracking site, so water needs to be transported in,
which can have significant economic and environmental costs.
In 2015, there was a moratorium (ban) on coal seam gas exploration and
fracking in Victoria. In September 2015, protestors rallied in the streets of
Melbourne to express their concerns about the process (see Figure 1.1.12). FIGURE 1.1.12

The Victorian Government agreed to examine the science and impact of the
CSG industry and methods while they extended their ban on the process.

CHAPTER 1 | FUELS 7
Propane and butane gases can be separated from natural gas by fractional
distillation. Propane and butane become liquids under pressure and are sold as
liquefied petroleum gas (LPG). LPG is used as a fuel in cars and in home gas
bottles. The natural gas remaining after the removal of propane and butane is used
widely as a fuel for home heating and cooking.

BIOFUELS
Governments and industry are exploring alternatives to fossil fuels in order to meet
our future energy needs and limit the impact of fossil fuels on the environment.
Ideally, new sources of energy will be renewable. Renewable energy is energy that
can be obtained from natural resources that can be constantly replenished.
Biochemical fuels (or biofuels) are fuels derived from plant materials such as
grains (maize, wheat, barley or sorghum), sugar cane (Figure 1.1.13) and vegetable
waste, and vegetable oils. The three main biofuels are biogas, bioethanol and
biodiesel. They can be used alone or blended with fossil fuels such as petrol
and diesel.

FIGURE 1.1.13

As well as being renewable, biofuels are predicted to have less impact on


the environment than fossil fuels. The plant materials used in the generation of
biofuels are produced by photosynthesis, which removes carbon dioxide from the
atmosphere and produces glucose (C6H12O6) in the following reaction:
6CO2(g) + 6H2O(l) → C6H12O6(aq) + 6O2(g)
The plants convert the glucose into cellulose and starch. Although carbon
dioxide is released back into the atmosphere when the biofuel is burnt, the net
impact should be less than for fossil fuels. You will compare fossil fuels and biofuels
in more detail in later sections of this chapter.

Bioethanol
For thousands of years, humans have employed biological catalysts (enzymes)
from yeasts to convert starches and sugars to ethanol. Enzymes catalyse the
breakdown of the starch in grain crops (such as barley and wheat) to glucose. Other
enzymes in yeasts then convert glucose and other small sugar molecules to ethanol
(CH3CH2OH) and carbon dioxide in the fermentation reaction:
C6H12O6(aq) → 2CH3CH2OH(aq) + 2CO2(g)

8 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Bioethanol is used extensively in Australia. This includes E10 petrol, which
contains 10% ethanol. This mix can be used by most modern car engines and its
use reduces the consumption of petrol derived from crude oil.

Biogas
Biogas is gas that is released in the breakdown of organic waste by anaerobic
bacteria. These bacteria decompose the complex molecules contained in substances
such as carbohydrates and proteins into the simple molecular compounds carbon
dioxide and methane. A digester (Figure 1.1.14) is a large tank filled with the
anaerobic bacteria that digest (consume) the complex molecules to form biogas.
manure and valve valve valve
farm waste
gas
outlet

rotting manure
and waste
vegetable methane gas
matter

methane
valve storage tank

solid
waste

FIGURE 1.1.14

A range of materials, including rotting rubbish (such as that seen in Figure 1.1.15)


and decomposing plant material, can be used to produce biogas.
The composition of biogas depends on the original material from which it is
obtained and the method of decomposition. The typical composition of a sample of
biogas is shown in Table 1.1.1.

TABLE 1.1.1

Gas Formula Percentage composition


(by volume)
FIGURE 1.1.15
Methane CH4 60

Carbon dioxide CO2 32

Nitrogen N2 4.5

Hydrogen sulfide H2S 2

Oxygen O2 1

Hydrogen H2 0.5

As you can see from Table 1.1.1, biogas consists mainly of methane and carbon
dioxide. Biogas can be used for heating and to power homes and farms. There are
more than 7 million biogas generators in China. Biogas generators are particularly
suited to farms, as the waste from a biogas generator makes a rich fertiliser.
In the future, it is likely more energy will be obtained from biogas generated
at sewage works, chicken farms, piggeries and food-processing plants. Your local
rubbish tip also has the potential to supply biogas. The gas can be used directly for
small-scale heating or to generate electricity.

CHAPTER 1 | FUELS 9
Biodiesel
Biodiesel is a mixture of organic compounds called esters.These esters are produced
by a chemical reaction between vegetable oils or animal fats and an alcohol (most
commonly methanol (CH3OH)).
The usual raw material for the production of biodiesel is vegetable oil from
sources such as soyabean, canola or palm oil. Recycled vegetable oil or animal
fats can also be used. The structure of a typical biodiesel molecule is shown in
Figure 1.1.16. (The production of biodiesel is discussed in section 1.3 on page 24.)
H H H H H H H H H H H H H H H O

H C C C C C C C C C C C C C C C C H

H H H H H H H H H H H H H H H O C H

FIGURE 1.1.16
H

1.1 Review
SUMMARY

• A fuel is a substance with stored energy that can be • Bioethanol can be produced by fermentation of
released relatively easily for use as heat or power. starches and sugars.
• A fuel is considered to be non-renewable if it cannot • Biodiesel is produced in a reaction between a
be replenished at the rate at which it is consumed. vegetable oil or an animal fat and a small alcohol
Fossil fuels such as coal, oil and natural gas are molecule such as methanol.
non-renewable. • Some of the non-renewable and renewable fuels
• Fossil fuels are produced over millions of years by in use in Australia are listed in Table 1.1.2.
the breakdown of biomass at high temperatures and
pressures underground. Australia has large reserves TABLE 1.1.2

of coal and natural gas.


• A fuel is considered to be renewable if it can be Non-renewable fuels Renewable fuels
replenished at the rate at which it is consumed.
Coal Bioethanol
Biofuels such as biogas, bioethanol and biodiesel Oil Biogas
are renewable. Liquefied petroleum gas (LPG) Biodiesel
• Biogas is formed by the anaerobic breakdown of Natural gas
Coal seam gas (CSG)
organic waste.

KEY QUESTIONS

1 What is the difference between a renewable and non-renewable fuel?


2 Give an example of a renewable fuel source and a non-renewable fuel source
used in Australia.
3 In Australia, which resource is likely to last longer before it is depleted: coal, oil
or natural gas? Explain your answer.
4 Wood from forests is a renewable resource that supplied global energy needs
for thousands of years.
a Why is wood no longer sustainable as the major energy source for today’s
society?
b Is it possible to have a non-renewable and sustainable energy source?
Explain.
5 Why is it necessary to treat crude oil by fractional distillation?

10 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


1.2 Fossil fuels and biofuels
Fuels contain stored chemical energy that can be harnessed to perform useful
functions. The heat energy released when fuels are burnt provides heat for warmth
and cooking, as well as acting as the source of electrical energy and mechanical
energy for transport.
In this section, you will look at the different fuels used to produce electricity or
power vehicles and compare the environmental impact of these fuels.

ENERGY TRANSFORMATIONS
All substances contain chemical energy. The chemical energy of a substance is
referred to as its energy content. Fuels are examples of substances with high
energy contents.
When fuels are used, their chemical energy is converted to a different form
of energy. For example, a competitive cyclist may eat energy bars. Much of the
chemical energy of the food is converted in the cyclist’s body to mechanical and
kinetic energy.
The conversion of chemical energy to kinetic energy in the cyclist is an example
of an energy transformation—energy is converted from one form to a different
form. The use of fuels involves energy transformations. The chemical energy in a
log on a fire can be converted to thermal energy to heat a room of a house.

FIGURE 1.2.1

When energy transformations occur, the total amount of energy is unchanged


because energy cannot be created or destroyed. However, not all of the energy is
converted to one specific form. In the case of the solar power cells shown in Figure
1.2.1, not all of the energy of the sunlight is converted to electrical energy.
The term energy efficiency is used to describe the percentage of energy from
a source that is converted to useful energy. For example, if the efficiency of a solar
panel on a roof is listed as 17%, it means that 17% of the energy arriving on the panel
from the Sun is transformed to electrical energy. The other 83% is converted to
other forms of energy. The largest proportion of the Sun’s energy reaching the solar
cells is converted into heat energy that simply increases the temperature of the cells.
CHAPTER 1 | FUELS 11
ELECTRICITY PRODUCTION
Chemical energy from most fuels is harnessed through combustion of the fuel.
In combustion reactions, the reactant combines with oxygen to produce carbon
dioxide and water. Thermal energy released from the combustion of fuels can be
converted into electrical energy. In Australia, electrical energy is produced from
several different fuels.

Electricity from coal


The combustion of coal generates over three-quarters of Australia’s electricity.
Rather than transport coal to every factory, office and household, the chemical
energy is converted to electrical energy at a power station. Electricity is transmitted
easily from the power station by metal cables and wires to other regions. The
reaction occurring when coal burns can be written as:
C(s) + O2(g) → CO2(g)
The energy released from the combustion of coal is about 32 kJ g–1.
A number of energy transformations occur in a coal-fired power station.
• Coal is burnt—chemical energy in coal is converted to thermal energy.
• Heat from the burning coal is used to boil water—thermal energy from the
burning coal becomes thermal energy in steam.
• Steam is passed through a turbine—thermal energy in the steam becomes
mechanical energy as the turbine spins. (This is the least efficient energy
transformation in the sequence.)
• Electricity is produced from a generator that is driven by the turbine—
mechanical energy is converted to electrical energy.
Figure 1.2.2 illustrates how the thermal energy released by the coal is converted
to electrical energy.

FIGURE 1.2.2

12 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


The overall efficiency of a coal-fired power station is 30–40%. The combustion
of brown coal is usually at the lower end of this efficiency range. Energy is lost
during each step of the process, mainly as heat.

Electricity from natural gas


Natural gas is also used in Victoria to generate electricity for the power grid. In a gas-
fired power plant, methane and other small alkanes are burnt to release energy. As
shown in Figure 1.2.3, the hot gases produced by combustion cause air to expand
in a combustion turbine to generate electrical energy. This is a simpler process than
in a coal-fired plant where the thermal energy is used to produce steam.

air exhaust

common shaft for


turbine/generator

generator

pressurised air Hot compressed


fuel gas spins turbine
combustion and generator.

fuel

FIGURE 1.2.3

The composition of natural gas varies but the main combustion reaction involves
methane. The equation is:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
The combustion of 1 mole of methane releases 890 kJ of energy, equivalent to
55.6 kJ g–1. This is a significantly higher value than that of coal.
A gas-fired plant is more efficient than a coal-fired power station, reaching
efficiencies just over 40%. Gas-fired plants also emit less carbon dioxide and
particulate matter (small solid particles of solid combustion products) per unit of
energy released. An added advantage of gas-fired plants is that the output can be
varied at short notice. This allows the operators to adjust to the fluctuating power
usage of consumers.
The largest gas-fired power station in Victoria, shown in Figure 1.2.4 (page 14),
is operated by Origin Energy at Mortlake in south-west Victoria. The plant uses
natural gas collected from off the nearby coast to generate electricity. Most Australian
states have gas-fired plants but many of the plants are small-scale ones. Coal seam gas
is the source of methane used in some states.

CHAPTER 1 | FUELS 13
FIGURE 1.2.4

Electricity from biogas


Biogas is a renewable fuel that can be used to generate electricity, usually in small-
scale electricity generators rather than large power plants. These smaller generators
are often located at the site where the biogas is produced. For example, sewage
works commonly burn biogas produced in a generator to supply some of their
power needs.
The main reaction occurring in the combustion of biogas is the same reaction
of methane burning in a gas-fired power station. The energy released per gram
of biogas is less than that of natural gas because the methane content in biogas is
significantly lower.
Berrybank Farm near Ballarat is an example of the innovative use of biogas.
Over $2 million has been spent on building infrastructure to collect the manure
from 20 000 pigs. The manure is fed into a digester that produces two useful
products: biogas and fertiliser. The biogas is used to fire generators, like the one
shown in Figure 1.2.5, that produce an estimated $180 000 of electricity annually.

(a) (b)

FIGURE 1.2.5

FUEL FOR TRANSPORT


Crude oil is the source of most of the fuel we use for transport. Crude oil is a mix
of alkanes. The alkanes in crude oil are separated into a series of fractions (parts)
by fractional distillation. Some of these fractions are important fuels, such as liquid
petroleum gas (LPG), petrol, kerosene and petrodiesel. LPG can also be separated
from natural gas.
14 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Petrol
Perhaps the most important of all hydrocarbon combustion reactions are those spark ignition
that occur when petrol is burnt. Petrol is a mixture of hydrocarbons, including
octane, and the combustion reactions of these chemicals power most of Australia’s
17.6 million motor vehicles. The equation for the combustion of octane is:
2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(l)
The combustion of 1 mole of octane releases 5450  kJ of energy, equivalent
to 47.8 kJ g–1. Combustion occurs in the cylinder of a car engine. The hot gases
formed push the piston in the engine, enabling the car to move. A typical piston is piston
shown in Figure 1.2.6.
The efficiency of a petrol engine in a new car can be as high as 25%. The
operation of a piston in a car engine can be seen in Figure 1.2.7.
crankshaft

FIGURE 1.2.6 H )

FIGURE 1.2.7

Liquid petroleum gas (LPG) can also be used in cars. Most of the vehicles that
use LPG as a fuel have a standard petrol engine with a fuel tank and fuel injection
system modified to suit a gaseous fuel. The equation for the combustion of propane,
a major component of LPG, is:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
The combustion of 1 mole of propane releases 2220 kJ of energy, equivalent to
50.5 kJ g–1.
In Australia, LPG is a significantly cheaper fuel than petrol, yet its popularity is
still limited. Some of the reasons for this are:
• most new vehicles are designed to run on petrol; therefore, the owner has to pay
around $2000 for a conversion
• the LPG fuel tank takes up boot space

CHAPTER 1 | FUELS 15
• there are fears that LPG cylinders might explode if the vehicle crashes
• the prices of fuels fluctuate, so often it is difficult to do meaningful price
comparisons.

Bioethanol
Australia imports over 90% of its fuel requirements. This reliance on other
countries, combined with concerns over the greenhouse emissions of fossil fuels,
has sparked interest in the production of the renewable biofuels, bioethanol and
biodiesel. Biodiesel is discussed in detail in the next section of this chapter.
Bioethanol can be produced from crops such as sugar cane. However, sugar
cane is also needed for sugar production so there are limits to the amounts of
bioethanol that can be produced in this way. Instead, researchers are trialling less
valuable sources of sugar and starch for bioethanol production.
The Manildra plant at Nowra in New South Wales, shown in Figure 1.2.8,
is one of Australia’s largest ethanol refineries. At this plant, flour and starch are
produced from wheat and sold for use in food manufacture. The waste that remains
still contains high levels of starch, which is converted to ethanol.

FIGURE 1.2.8

Ethanol can be blended with petrol for use in motor vehicles. Australian
government regulations limit the proportion of ethanol in petrol to 10%. This petrol
blend is labelled E10 and sold at most Australian service stations. The presence of
ethanol reduces the emissions of particulates and gases such as oxides of nitrogen,
but higher levels of ethanol can damage engines, especially in older vehicles.
The equation for the combustion of ethanol is:
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)
The combustion of 1 mole of ethanol releases 1367  kJ of energy, equivalent
to 29.7 kJ g–1. As Table 1.2.1 shows, the energy content of ethanol is about 62%
that of petrol, so a larger mass (and volume) of ethanol is required to provide
the same amount of energy. At a simple level, the lower energy content of ethanol
can be regarded as the result of the carbon atoms in an ethanol molecule being
partly oxidised (‘partly burnt’). This is due to the presence of oxygen in the ethanol
molecule.
16 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
TABLE 1.2.1

Fuel Energy content (kJ g–1) Energy density (kJ L–1)


Methane 55.6 23 500 (liquefied)
Propane (LPG component) 50.5 29 400 (liquefied)
Butane (LPG component) 49.6 29 800 (liquefied)
Octane (petrol fraction) 47.8 33 400
Ethanol 29.7 23 400

ENVIRONMENTAL IMPACT
A discussion of the environmental impact of fuels needs to consider both the impact
of emissions from the combustion of the fuel, and the impact on the environment of
obtaining the fuel in the first place.

Emissions from fuel combustion


Carbon dioxide
Because large quantities of fuel are burnt every day to meet society’s energy needs,
the level of carbon dioxide production is high. This is a concern because carbon
dioxide is a greenhouse gas.
Energy from the Sun heats the surface of the Earth. The Earth in turn radiates
energy back towards space but greenhouse gases in the atmosphere absorb and
re-radiate the energy in a process known as the greenhouse effect. The higher the The greenhouse effect is
concentration of greenhouse gas, the more energy is trapped. caused by heat being trapped
in the Earth’s atmosphere by
The greenhouse effect occurs naturally due to the gases present in the
greenhouse gases, which causes
atmosphere. However, scientists are concerned that increasing levels of greenhouse
an increase in temperatures at the
gases produced by our use of fossil fuels are causing global warming and triggering
Earth’s surface. As the amount of
consequential shifts in weather patterns and climate. This is referred to as the greenhouse gases in the Earth’s
enhanced greenhouse effect. atmosphere increases due to
Methane, water vapour, nitrogen oxides and ozone are also greenhouse gases. human activities, more heat is
Methane is 21 times more effective at trapping heat than carbon dioxide. The way trapped, which is predicted to
in which greenhouse gases restrict heat radiation leaving the Earth is shown in
Figure 1.2.9.

Sun

Some solar radiation


Some heat escapes,
Earth's surface.
n

some is trapped by
io
at

greenhouse gases.
di

Solar radiation is
ra

absorbed by the
lar

Earth's surface,
so

warming it.
e
ioxid
on d
carb
ni
tro
us
coal, oil, petrol ox
id
ns

e
lo

fertiliser
ha

cattle,
me

aerosols, rice paddies


tha

Atmosp
ne
CFCs

refrigerators These products are


all sources of
Earth

greenhouse gases.
here

FIGURE 1.2.9

CHAPTER 1 | FUELS 17
The graph shown in Figure 1.2.10 supports concerns that the Earth is warming.
Many countries are choosing alternatives to fossil fuels to address these fears.
Projection

6.0
5.5
5.0
4.5
4.0

Temperature change (°C)


3.5
3.0
2.5
2.0
1.5
1.0
0.5
(13.7)
–0.5
–1.0
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100
Year

FIGURE 1.2.10

Each fuel discussed in this section produces carbon dioxide when it burns. Table
1.2.2 compares the theoretical mass of carbon dioxide produced from the complete
combustion of 1 gram of each fuel and per unit of energy produced.

TABLE 1.2.2

Fuel Mass of CO2 (g) emitted Mass of CO2 (g) per


per gram of fuel megajoule of energy
produced (approx.)

Coal 3.7 93

Natural gas 2.8 56

LPG 3.0 65

Petrol 3.1 73

Ethanol 1.9 72

Bioethanol is a renewable fuel derived from plants. Although carbon dioxide is


produced when bioethanol burns, carbon dioxide is also absorbed by the plants as
they grow. For this reason, the widespread use of bioethanol should lead to a net
reduction in the levels of carbon dioxide emitted.
However, bioethanol is not carbon neutral. This is because energy is required,
and emissions are produced, in the growing, transport and refining of the fuel. Note
also that although a relatively low mass of carbon dioxide is emitted per gram of
fuel burnt, because bioethanol produces much less energy than the same mass or
volume of petrol, a similar mass of carbon dioxide is emitted to produce the same
quantity of energy.

18 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


CHEMFILE
Cleaner coal

• removing water from brown coal by heating; the volatile hydrocarbons that are
driven off are also burnt to produce electricity

There are several methods for converting coal to liquid and gaseous fuels. Flash
pyrolysis has been developed by CSIRO for converting coal to oil. In this process,
crushed coal is heated to 600°C. The tar that forms is reacted with hydrogen to give

Other emissions
Carbon dioxide and water vapour are not the only products formed when fuels
are burnt. Fuels may contain elements such as sulfur, which burns to form sulfur
dioxide, or the high temperatures of combustion can lead to reactions with nitrogen
in air. Table 1.2.3 lists the more common pollutants formed.

TABLE 1.2.3

Emission Formation Comments

Sulfur dioxide (SO2) Sulfur in fuel reacts with Causes respiratory


oxygen: problems. Leads to the
S(s) + O2(g) → SO2(g) formation of acid rain

Nitrogen oxides Nitrogen in fuel reacts Causes respiratory


(NO and NO2) with oxygen, or nitrogen problems. Leads to
in air reacts due to high the formation of other
temperatures: pollutants and acid rain
N2(g) + O2(g) → 2NO(g)
2NO(g) + O2(g) → 2NO2(g)

Ozone (O3) Nitrogen oxides react with Causes respiratory


oxygen at high temperatures problems

Particulates, such as ash Combustion of impurities Irritant. Adheres to houses


in fuel and plants

Carbon monoxide Incomplete combustion of Poisonous gas


fuel

Organic chemicals such as Reactions of other organic Toxic and carcinogenic


methanal and ethanal chemicals in fuel compounds

The levels of each pollutant mentioned in Table 1.2.3 vary with the composition
of the fuel and the efficiency of the particular combustion process. However, it is
possible to generalise.
• Ash is usually more of a problem with coal than other fuels. Ash is produced
when coal is burnt without any purification or removal of impurities.
• Sulfur levels are lower in natural gas and LPG than in liquid or solid fossil fuels.
• The molecules in petrol are larger than the molecules in natural gas, LPG and
ethanol. As a consequence, the combustion of petrol tends to be less complete.
This produces more carbon monoxide and particulates.
• Although biofuels are renewable, they can still produce the same pollutants as
fossil fuels when burnt.

CHAPTER 1 | FUELS 19
All fuels have to be mined or produced and the environmental impact of sourcing
a fuel needs to be considered. Table 1.2.4 shows some of the sources of the fuels
described in this chapter.

TABLE 1.2.4

Fuel source Notes

Biogas is often collected from sewage farms


and rubbish tips. The gas collection minimises
emissions associated with these sites. Because
methane is much more effective as a greenhouse
gas than carbon dioxide, it is better to collect the
methane in biogas and combust it to produce
carbon dioxide than to release it directly to the
atmosphere.

Oil rigs, once in place, can operate with low impact


on the environment but the issues created when
a spill or explosion occurs can be significant.

Oil rig
Coal mines can be open cut or underground.
Open-cut mines, such as in the Latrobe Valley in
Victoria, are damaging to the local environment.

Bioethanol is produced from crops. Growing


crops requires energy expenditure and the use of
resources such as water and fertiliser. Intensive
farming can lead to land degradation and erosion.
These are larger issues if crops are grown solely to
produce ethanol, but of less concern if waste from
food crops is used as a raw material. Diverting
crops from fuel production could also drive up the
cost of food produced from those crops.

20 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


CHEMFILE
The Hazelwood coal mine fire
On a very hot day, on 9 February 2014, the Hazelwood open-

permanent damage to the lungs and circulatory systems.

• vulnerable residents were evacuated from nearby Morwell


• school children were transported to schools further from

• residents were advised to stay indoors.

FIGURE 1.2.11

RENEWABILITY
Fossil fuels are a non-renewable source of energy. It took millions of years for their
formation in the Earth’s crust, so the likelihood of new deposits forming cannot be
considered. The reserves of each fossil fuel are summarised below.
• Coal—reserves are extensive but low efficiency and concerns about emissions
are making coal increasingly less popular as a fuel.
• Crude oil—reserves are more limited than those of coal and availability is likely
to decline in coming decades.
• Natural gas—deposits are likely to be exhausted over the coming decades but
reserves of coal seam gas and shale gas could potentially provide natural gas into
the next century. Concerns over fracking need to be resolved if natural gas is to
be sourced from these reserves.
Biofuels are renewable and current production levels are sustainable. However,
biofuels produce only a small percentage of Australia’s fuel needs.
If biofuel production were to increase significantly, we could need to grow crops
specifically for this purpose. This would present a number of issues, including
land degradation, clearing of forest and bushland, and ensuring food supplies
are maintained.
CHAPTER 1 | FUELS 21
1.2 Review
SUMMARY

• Fuels such as petrol, natural gas, biogas and • The combustion of fuels produces a range of other
bioethanol undergo combustion reactions in excess pollutants such as carbon monoxide, sulfur dioxide,
oxygen to form carbon dioxide and water. nitrogen oxides and particulates.
• The combustion reactions of fuels are used to • Petrol produces more energy per gram than LPG or
produce electricity and to power vehicles. bioethanol. However, bioethanol and LPG produce
• In a coal-fired power station, thermal energy from less carbon dioxide and particulates in emissions.
coal creates steam that is used to turn a turbine and • Biofuels offer several environmental advantages:
generate electricity. The efficiency of this process is CO2 is absorbed during the growth of crops used in
between 30 and 40%. their production, they can be replenished and they
• Electricity can also be produced from the can be produced from material that would have
combustion of natural gas or biogas. otherwise been waste.
• Petrol engines can use petrol or petrol blended • A shift to large-scale production of biofuels could
with ethanol. Engines can also be modified to run place a strain on resources and available farmland.
on LPG. • Table 1.2.5 compares the advantages and
disadvantages of some fuels.

TABLE 1.2.5

Fuel Advantages Disadvantages

Coal • Large reserves • Non-renewable


• Less easily transported than liquid or gaseous fuels • High level of emissions
• Relatively high energy content

Natural gas • More efficient than coal for electricity production • Non-renewable
• Easy to transport through pipes • Limited reserves
• Relatively high energy content • Polluting but less than coal and petrol

Biogas • Renewable • Low energy content


• Made from waste • Supply of waste raw materials limited
• Reduces waste disposal
• Low running costs
• CO2 absorbed during photosynthesis

Petrol • High energy content • Non-renewable


• Ease of transport • Polluting but less than coal
• Limited reserves

LPG • Low cost • Non-renewable


• Easily separated from natural gas • Polluting but less than petrol
• Relatively high energy content; fewer particulates
produced than petrol

Bioethanol • Renewable • Limited supply of raw materials from which to


• Can be made from waste produce it
• CO2 absorbed during photosynthesis • Lower energy content than petrol
• Burns smoothly • May require use of farmland otherwise used for
• Fewer particulates produced than petrol food production

22 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


KEY QUESTIONS

1 The following processes are all part of the production of electrical energy
from coal. Arrange these processes in order of occurrence.
• Energy released from coal is transferred to water.
• Steam spins a turbine.
• Coal is added to a furnace.
• Coal is excavated, crushed and dried.
• Steam is produced.
• Electricity is generated.
2 Classify each of the following as an advantage or a disadvantage of the use
of bioethanol compared to petrol as an energy source.
a Less CO2 impact overall
b Lower energy content (kJ g–1)
c Can be produced from waste products
d Renewable resource
e Greater amount of CO2 emitted to travel a set distance
3 Methane can be sourced from crude oil, coal seam gas, sewage and
gas wells.
Complete the following table that describes the sources of methane and the
process used to extract or separate the methane.

Source Composition of Extraction process


source

Crude oil

Coal seam gas

Sewage

Gas well

4 a The water content of brown coal is 60–70%. What implications does this
high water content have for the energy released from burning the coal?
b What pre-treatment could raise the energy content per gram of brown
coal consumed in a power station?
c If some electricity produced from burning coal was used to reduce its
water content, then how could this energy cost be minimised?
d What impact do impurities such as sulfur have on generating electricity
from brown coal?

CHAPTER 1 | FUELS 23
1.3 Petrodiesel and biodiesel
The high energy content of diesel makes it an excellent fuel for transportation
and equipment designed to do heavy work. For many years, petrodiesel, which
is produced from crude oil, has been the primary source of fuel for diesel engines.
Some of the uses of diesel in transport are in ocean liners, farming machinery and
the engines that provide the energy for the large hauling capacity of mining trucks
(Figure 1.3.1).
In the last 20 years, biodiesel has emerged as an alternative to petrodiesel. In this
section, you will compare the sourcing, performance and environmental impact of
these two fuels.

(a) (b) (c)

FIGURE 1.3.1

CHEMFILE
Rudolf Diesel

oils and would help considerably in the development of agriculture of the countries which
use it.’
FIGURE 1.3.2

petroleum and the coal tar products of the present time.’

DIESEL PRODUCTION AND STRUCTURE


A diesel engine is a form of internal combustion engine that does not require a spark
to ignite the fuel in the engine cylinder. Diesel engines are favoured in situations
requiring high fuel efficiencies and for heavy haulage vehicles.
Diesel engines have a 20–40% better fuel economy than petrol engines because:
• diesel engines are typically more energy efficient than petrol engines
• diesel fuel has a higher density than petrol, so although the energy content of
diesel and petrol, measured in kJ g–1, is similar, diesel fuel yields more energy
per litre.
The most common form of diesel fuel is petrodiesel, which is produced from
crude oil. However, biodiesel is increasingly being manufactured as an alternative.
The two pathways for producing diesel are shown in Figure 1.3.3.

24 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


fat or oil converted to biodiesel crude oil—petrodiesel obtained by
fractional distillation

H H H H H H H H H H H O H H H H H H H H H H H H
H C C C C C C C C C C C C H H C C C C C C C C C C C C H
H H H H H H H H H H H O C H H H H H H H H H H H H H

biodiesel H petrodiesel

diesel engine

FIGURE 1.3.3

Petrodiesel
Petrodiesel is one of the products of the fractional distillation of oil. It is not a
pure substance. Different manufacturers produce petrodiesel of different
compositions, but petrodiesel is generally around 75% alkanes and 25% aromatic
hydrocarbons. The alkanes range from C10H22 to C15H32. Aromatic hydrocarbons
contain molecules made up of six-membered carbon rings with alternating single
and double bonds. You can see the structures of both alkanes and aromatic
hydrocarbons found in petrodiesel in Figure 1.3.4.
H H

H H H H H H H H H H H H C C
H H
C C C
H C C C C C C C C C C C C H
C C C
H C C H
H H H H H H H H H H H H
dodecane
H H
naphthalene
FIGURE 1.3.4

CHAPTER 1 | FUELS 25
Biodiesel
O Fats and oils are triglycerides with a molecular structure consisting of three
hydrocarbon chains attached by ester functional groups to a backbone of three
H2C O C (CH2)14CH3 carbon atoms, as shown in Figure 1.3.5.
O The triglyceride is converted into biodiesel by warming it with an alcohol,
usually methanol, in a process known as transesterification. Potassium hydroxide
HC O C (CH2)14CH3 solution acts as a catalyst in this reaction. A catalyst is a substance that increases
O
the rate of a reaction without being consumed itself.
In the transesterification reaction, the triglyceride is converted into a small
H2C O C (CH2)14CH3 molecule called glycerol and three ester molecules with long carbon chains. The
ester molecules are the biodiesel product. The reaction is shown in Figure 1.3.6.
FIGURE 1.3.5

H O
H
H C O C (CH2)14CH3
O H C OH

H C O C (CH2)14CH3 + 3CH3OH H C OH + 3CH3(CH2)14COOCH3


O
H C OH
H C O C (CH2)14CH3
H
H

triglyceride methanol glycerol fatty acid methyl esters


(palm oil) (biodiesel)

FIGURE 1.3.6

The structure of a typical biodiesel molecule is shown in Figure 1.3.7. Molecules


of this type are sometimes referred to as fatty acid esters, because carboxylic
acids with relatively long hydrocarbon chains are referred to as fatty acids.
H H H H H H H H H H H H H H H O

H C C C C C C C C C C C C C C C C H

H H H H H H H H H H H H H H H O C H

FIGURE 1.3.7 H

Like petrodiesel, biodiesel is not a pure substance. The structure of the


triglyceride varies depending on the particular plant or animal used as the source.
Triglycerides produced by animals, such as tallow, usually form saturated esters,
which have only carbon–carbon single bonds in the hydrocarbon chain. However,
triglycerides produced by plants often form unsaturated esters like the one
shown in Figure 1.3.8.
H H H H H H H H H H H H H H O

H C C C C C C H C C C C C C C C C H

H H H H H C C C H H H H H H H O C H

H H H H
FIGURE 1.3.8

26 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


The term ‘saturated’ refers to hydrocarbons that contain only single bonds
between the carbon atoms. They are said to be saturated because each
carbon atom is bonded to as many hydrogen atoms as possible. ‘Unsaturated’
means that there is at least one carbon–carbon double or triple bond within

The presence of double bonds in the hydrocarbon chain changes the shape of
the molecules, making it more difficult for them to pack together. This weakens
the dispersion forces between neighbouring molecules of unsaturated esters. As
a result, biodiesel produced from plant oil usually has a lower melting point than
biodiesel produced from animal fats.
At present, far more petrodiesel is consumed than biodiesel, both locally and biodiesel (7%)
internationally (Figure 1.3.9). Australia’s total diesel consumption is over 23 000
megalitres of diesel per year. Biodiesel comprises only 400 megalitres of this total.
This gap is likely to close in the future as the biodiesel industry is the subject of
extensive scientific research.

COMPARISON OF PETRODIESEL AND BIODIESEL

Some of the properties of petrodiesel and biodiesel are compared in Table 1.3.1. petrodiesel (93%)

TABLE 1.3.1

Property Explanation of property Petrodiesel Biodiesel FIGURE 1.3.9


–1
Density (kg L ) Mass of fuel in a given 0.84 0.87
volume

Viscosity (cSt) Measure of a fluid’s 2.5 4.9


resistance to flow at 40°C

Cloud point (°C) Lowest temperature at –15 to 5 –3 to 12


which crystals start to form

Energy content (kJ g–1) Energy released per gram 48 41


of fuel

Energy density (kJ L–1) Energy released per litre 40 36


of fuel

The energy contents of petrodiesel and biodiesel are comparable and also
similar to that of petrol (47 kJ g–1). However, because both forms of diesel have
higher densities than petrol, the energy released per litre of diesel fuel is higher than
for petrol (34 kJ L–1).
Examination of the data in Table 1.3.1 assists in understanding the following
key points.
• Petrodiesel produces up to 10% more energy than biodiesel (this is offset by the
fact that biodiesel burns more smoothly and efficiently).
• Biodiesel has a higher viscosity than petrodiesel. Biodiesel does not flow as
easily along fuel lines and through filters.
• In very cold climates, biodiesel can lose its ability to flow, or worse still, it can
solidify. The cloud point is a measure of performance at low temperature.
Cloud point refers to the temperature at which small crystals start to form.
Obviously, an engine will not run if the fuel will not flow on a cold day.
The differences in viscosity and flow under cold conditions are related to
the chemical structures of the two forms of diesel. Petrodiesel consists of smaller,
non-polar molecules (see Figure 1.3.10, page 28). The only forces present between
neighbouring petrodiesel molecules are weak dispersion forces.
However, the hydrocarbon chain in biodiesel is often longer and each molecule
also contains two highly electronegative oxygen atoms (see Figure 1.3.10).

CHAPTER 1 | FUELS 27
H H H H H H H H H H H H

H C C C C C C C C C C C C H

H H H H H H H H H H H H
petrodiesel

H H H H H H H H H H H H H H H O

H C C C C C C C C C C C C C C C C H

H H H H H H H H H H H H H H H O C H

biodiesel
H
FIGURE 1.3.10

The oxygen atoms create dipoles at one end of the molecule, with the result that
dipole–dipole bonds form between neighbouring molecules. These stronger
intermolecular bonds cause the viscosity and melting point of biodiesel to be greater
than for petrodiesel.
The presence of polar bonds in biodiesel molecules also explains why biodiesel
has a greater tendency than petrodiesel to absorb water. Water is a polar molecule
and is more attracted to the slightly polar biodiesel molecules than to non-polar
petrodiesel molecules. A substance that absorbs water easily is said to be more
hygroscopic than one that does not. The water content of biodiesel needs to be
low for efficient combustion to occur.
For the motorist, the differences in the properties of the two fuels imply that:
• diesel blends containing up to 20% biodiesel have a similar performance to
petrodiesel and the engines do not need to be modified
• in cold climates, additives need to be added to motor fuel containing high levels
of biodiesel. Service stations also need to ensure the pump is kept warmer than
the surroundings. Biodiesel sourced from plants has fewer cold-flow issues than
biodiesel produced from animal fats.
Biodiesel also has the potential to keep fuel systems cleaner, but higher
quality seals and fuel hoses may be required. Biodiesel cannot be stored for as
long as petrodiesel because it is more likely to react with atmospheric oxygen and
biodegrade. Biodegradation is the breakdown of a substance by the action of
living organisms, such as bacteria and fungi.

When comparing the two forms of diesel, you need to consider the emissions
produced when the fuels are burnt, as well as the impact on the environment of
producing the fuel in the first place.
Combustion and emissions
The main combustion products of both forms of diesel are carbon dioxide and
water. The combustion reactions of typical components of the fuels are represented
by the equations:
Petrodiesel: 2C12H26(l) + 37O2(g) → 24CO2(g) + 26H2O(g)
Biodiesel: 2C17H34O2(l) + 49O2(g) → 34CO2(g) + 34H2O(g)
The carbon dioxide emissions from both petrodiesel and biodiesel are about
73 g MJ–1, which is almost the same as for petrol. However, diesel vehicles produce
10–20% less carbon dioxide emissions than petrol vehicles because of their higher
fuel efficiency. In the case of biodiesel, carbon dioxide is absorbed in the growth
of the plant or animal the biodiesel is derived from, reducing the net impact on
greenhouse gas levels.
28 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
As with petrol engines, use of either form of diesel leads to emissions of pollutants
such as nitrogen oxides, carbon monoxide and unburnt hydrocarbons.
Petrodiesel also produces some sulfur dioxide (SO2) emissions. Whether
biodiesel produces SO2 depends upon the origins of the triglycerides that it is
produced from. For example, soyabean oil does not contain sulfur but canola
oil does.
Biodiesel exhaust contains up to 20% less particulate matter than diesel.
There is considerable debate about which fuel, diesel or petrol, is the cleanest in
terms of emissions. The answer is not clear-cut. Diesel engines produce less carbon
dioxide, carbon monoxide and unburnt hydrocarbons. But petrol engines produce
virtually no particulates and emit less nitrogen oxides.
Fuel production and the environment
Both types of diesel impact on the environment from where they are sourced and
the environment around the industrial plants where they are refined. Some of these
impacts are illustrated in Table 1.3.2.

TABLE 1.3.2

Petrodiesel Biodiesel

Impacts of
sourcing

• Crude oil can be mined on land or at sea. • Increased biodiesel production requires intensive farming.
• Crude oil is non-renewable. • Crops such as canola are renewable because they can be
• Oil deposits are often located in environmentally sensitive harvested each year.
locations and mining approval is often contested. • Growing crops requires resources such as water and
• Spills or leaks could significantly damage local ecology. fertiliser. The quality of the soil deteriorates if the same
• Oil is a flammable liquid with associated fire risks. crops are grown each year.
• Farm machinery produces CO2 and other pollutants that
reduce the net benefits of renewable fuels.
• High-quality farmland is used for growing fuels instead
of food.

Impacts of
production

• Oil refineries can produce significant emissions due to the • Biodiesel plants should produce less emissions than oil
burning of excess hydrocarbons. refineries do.
• Energy is required to operate the refinery. • Energy is required to operate the plant.

CHAPTER 1 | FUELS 29
In the immediate future, the growth of biodiesel production may depend upon
economics. If biodiesel manufacturers cannot produce biodiesel from canola for
a price lower than the market price of petrodiesel, then the industry is unlikely to
expand. A complicating factor is the fluctuations that occur in the price of diesel as
shown in Figure 1.3.11.

120.00
98.46
100.00

Price (cents per litre)


80.00
73.33
60.00

40.00 36.13

32.39
20.00

0.00 4.74

1973–74
1975–76
1977–78
1979–80
1981–82
1983–84
1985–86
1987–88
1989–90
1991–92
1993–94
1995–96
1997–98
1999–00
2001–02
2003–04
2005–06
2007–08
2009–10
2011–12
Financial year

FIGURE 1.3.11

EXTENSION

Biodiesel production using alternative


feedstocks
Several innovative Australian companies are successfully trialling new processes
to avoid using food-grade crops as the source of triglycerides for biodiesel.
• Biomax in Laverton, Victoria, produces biodiesel from poppy seed oil.
(a)
Tasmania has a licence to grow opium poppies for the production of morphine.
The company was not allowed to sell the oil on the open market due to fears
it might contain illegal substances. However, they were permitted to make
biodiesel from oil that would otherwise have been a waste product.
• Biomax is also involved in a trial in Victoria’s Latrobe Valley at a cooling
pond for a power station. Carbon dioxide produced in the coal-fired power
station nearby is used to promote the growth of algae with a high oil content
(Figure 1.3.12a).
• Australian Renewable Fuels Limited manufactures 150 million litres of biofuel
(b)
each year at a northeastern Victorian plant in Barnawartha. The raw materials
FIGURE 1.3.12 are tallow from local abattoirs and used cooking oil, which would otherwise be
difficult to dispose of.
• Juncea (a close relative to canola) and agave crops are being trialled on
marginal farmland in several locations (Figure 1.3.12b). These crops have
a high oil yield but don’t have to grow on farmland that could be used for
food crops.

30 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


1.3 Review
SUMMARY

• Diesel engines are used in many forms of transport and in heavy-duty equipment.
• Diesel engines have a better fuel economy than petrol engines because diesel has a
higher energy efficiency and higher energy per litre.
• Diesel engines typically produce 10–20% less carbon dioxide emissions than petrol
engines.
• Diesel fuel can be separated from crude oil by fractional distillation (petrodiesel)
or synthesised from the triglycerides in plants or animals (biodiesel).
• Petrodiesel is a non-renewable fuel, whereas biodiesel is a renewable fuel.
• Petrodiesel is composed of about 75% alkanes containing 10–15 carbon atoms
(see Figure 1.3.13) and 25% aromatic compounds.

H H H H H H H H H H H H

H C C C C C C C C C C C C H

H H H H H H H H H H H H
FIGURE 1.3.13

• Biodiesel is produced from triglycerides in animal fats or plant oils. The triglycerides
react with methanol in a transesterification reaction to form biodiesel (see Figure 1.3.14).
H O
H
H C O C (CH2)14CH3
O H C OH

H C O C (CH2)14CH3 + 3CH3OH H C OH + 3CH3(CH2)14COOCH3


O
H C OH
H C O C (CH2)14CH3
H
H

triglyceride methanol glycerol fatty acid methyl esters


(palm oil) (biodiesel)

FIGURE 1.3.14

• Biodiesel molecules can be described as fatty acid esters.

CHAPTER 1 | FUELS 31
• Table 1.3.3 compares petrodiesel with biodiesel.

TABLE 1.3.3

Property Petrodiesel Biodiesel

Renewability Non-renewable Renewable

Energy content Marginally higher Marginally lower

Viscosity Lower Higher

Cold flow Can be used without additives at lower More likely to need antifreeze additives
temperatures than biodiesel. when used in cold climates.

Emissions Produces CO2, particulates and other Produces CO2 but CO2 is consumed in
pollutants. production of the triglycerides used to
make the fuel. Produces fewer particulates.
Produces other pollutants.

Environmental impact of Oil fields are prone to spills and Biodiesel produced from farm crops can
production damage to local habitats. Oil refineries add to land degradation and might lead to
produce emissions that have a negative higher food prices. Biodiesel made from
impact on local regions. waste products such as used cooking oil has
a positive impact on the environment.

KEY QUESTIONS

1 Select the correct statement about petrodiesel.


A Petrodiesel is a renewable fuel as it is formed from plants.
B Petrodiesel is purified to ensure all molecules include the same number
of carbon atoms.
C Petrodiesel is a mixture of substances including LPG and petrol.
D Petrodiesel contains 75% alkanes with 10–15 carbon atoms.
2 What is the name of the reaction in which a triglyceride is broken down
to form biodiesel molecules?
3 Determine if the following statements about biodiesel are true or false.
a Biodiesel can contain several different compounds.
b Biodiesel molecules contain ester groups.
c Biodiesel is an alkane.
d Three molecules of biodiesel can be obtained from each molecule
of a triglyceride.
e All hydrocarbon chains in biodiesel molecules are saturated.
f Biodiesel is formed in a transesterification reaction.
4 Why are the CO2 emissions from the use of biodiesel not considered
as problematic as those produced from the use of petrodiesel?

32 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Chapter review
KEY TERMS

acid rain combustion fossil fuel


alkane dipole–dipole bond fracking
anaerobic dispersion force fractional distillation
aromatic hydrocarbon electronegative fuel photosynthesis
biodegradation energy content greenhouse effect renewable
biodiesel energy efficiency greenhouse gas saturated ester
bioethanol energy transformation homologous series shale gas
biofuel enhanced greenhouse hydrocarbon sustainable
biogas effect hygroscopic transesterification
carbon neutral enzyme liquefied petroleum gas triglyceride
catalyst fatty acid natural gas unsaturated ester
cloud point fatty acid ester non-renewable viscosity
coal seam gas fermentation petrodiesel

Types of fuels Fossil fuels and biofuels


1 The world has become very dependent on the 8 The following energy sources are used across
products of the petrochemical industry, but the raw the world: coal, bioethanol, biodiesel, natural gas.
materials of crude oil and natural gas are likely to be Which one is likely to run out the fastest?
virtually exhausted by 2100. Assuming that current 9 Explain the term ‘energy efficiency’.
production remains unchanged and no alternative
10 What are some of the ways in which energy is lost,
sources are available, suggest the impact of the lack
leading to a reduced efficiency in a coal-fired power
of raw materials on our lifestyle.
station?
2 Refer to Figure 1.1.4 on page 3 to answer the following
11 Biogas, petrol and bioethanol are used to power
questions.
vehicles.
a In the year 2000, what type of fuel provided the
a List the fuels in order of their energy content per
most energy on a global scale?
gram (from highest to lowest). You may need to
b Rank the different fuels in order from most to refer to Table 1.2.1 on page 17.
least amount of energy expected to be produced
b The emissions of carbon dioxide per gram from the
in 2020.
combustion of bioethanol are less than that from
3 Why are fossil fuels considered to be non-renewable? octane (petrol). However, a car using bioethanol
4 Refer to Figure 1.1.5 on page 4 to answer the following produces more carbon dioxide when driving the
questions. same distance as a car using octane. Which one
a What type of coal takes the longest amount of time of the follow could be the best explanation for this
to form? difference?
b Of peat, brown coal and black coal, which releases A Bioethanol is more efficient than octane.
the least amount of heat energy? B The energy content of bioethanol is less than
c Which type of coal is a better quality fuel? that of octane.
5 Refer to Table 1.1.1 on page 9, which lists the typical C The temperature of the engine favours the
composition of biogas. combustion of octane.
a What two gases form the largest percentage of a D More energy transformations are required in
typical biogas sample? the combustion of bioethanol.
b Why are there variations in the percentage of gases 12 Explain why bioethanol is sometimes described as
making up different samples of biogas? a ‘carbon neutral’ fuel. Use chemical equations for
6 What types of vegetable oils is biodiesel commonly photosynthesis, fermentation and combustion to
sourced from? support your answer.
7 When coal contains a greater amount of water (as 13 Use the terms ‘methane’, ‘oxygen’, ‘bacteria’ and
it does in peat and brown coal), why is less heat ‘carbon dioxide’ to explain the formation and
released when the coal is burnt? composition of biogas.

CHAPTER 1 | FUELS 33
14 a Explain what ‘E10 petrol’ means. 18 For each of the following scenarios, decide if it is more
b How does the introduction of E10 help with the likely to refer to petrodiesel or biodiesel.
potential shortage of crude oil? a A sample of diesel has gone cloudy after being
15 The fact that global warming is taking place is now stored a long time.
generally accepted. Conduct some research using b The exhaust from this engine contains significant
the internet to discover some of the consequences particulates.
of global warming. Give one example each of the c The car will not start on a cold morning.
effect on: d The water content of the fuel has reached a
a the polar ice caps high level.
b changing weather patterns
Connecting the main ideas
c crop production
19 Ethanol is produced industrially by reacting ethene
d extinction of plant or animal species.
with water using a phosphoric acid catalyst at 300°C:
Petrodiesel and biodiesel C2H4(g) + H2O(g) → CH3CH2OH(g)
16 Which one of the following is the most likely a Explain whether ethanol produced by this method
component of petrodiesel? is a biochemical fuel.
A Propene b Describe how ethanol, which is classified as a
B C3H8 biochemical fuel, could be produced.
C C11H24 20 Conduct some research on the internet to find out
D C16H24O2 which nations are the top ten consumers of energy.
17 Trials are being conducted to source biodiesel from 21 The 2015 Paris Agreement was an international
algae grown in the warm water of a power station response to global warming in which all nations
cooling pond. The water is warm and carbon dioxide were asked to commit to keeping the global average
emitted from the power station can be trapped and temperature rise to below 2°C, through reductions in
bubbled through the water to enhance the growth greenhouse gas emissions.
of the algae. Classify the following as advantages or a What impact would adoption of the Paris
disadvantages of large-scale production of biodiesel Agreement have on Australia?
from algae. b Discuss the role that biofuels could play in helping
a Fewer particulate emissions than petrodiesel Australia meet its target for reducing greenhouse
b Renewable gas emissions.
c Less reliance on fossil fuels
d Distribution outlets required
e Fewer net CO2 emissions than petrodiesel
f Oil can be ‘harvested’ many times per year
g Reduction of CO2 emissions from coal-fired power
stations
h More additives need to be added to the fuel in cold
climates

34 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


CHAPTER

Energy from fuels

Before the invention of agriculture, a person in an early hunter-gatherer society


used approximately 10 MJ of energy per day. Despite being less active than
hunter-gatherers, a person in our modern industrial society uses, on average,
nearly 1000 MJ per day. This figure is 100 times greater than the body’s basic
requirement. The bulk of our energy use comes from the combustion of fuels,
which we use directly or indirectly. Some of our activities use small amounts of
energy. Others, such as the launching of a space shuttle, use enormous amounts
of energy.
In Chapter 1 you learned about the different fuels available to meet current
transport, heating and cooking requirements across the globe. By the end of this
chapter, you will have a greater understanding of the way in which energy changes
that occur as a result of combustion of fuels can be represented when writing
chemical equations and by drawing energy profile diagrams. You will also learn
how the energy released by the combustion of different fuels can be measured.

Key knowledge
• The comparison of exothermic and endothermic reactions including their
enthalpy changes and representations in energy profile diagrams
• Combustion of fuels as exothermic reactions with reference to the use of the
joule as the SI unit of energy and measurement of enthalpy change including
symbol (∆H) and common units (kJ mol–1, kJ g–1, MJ/tonne)
• The writing of balanced thermochemical equations, including states, for the
complete and incomplete combustion of hydrocarbons, methanol and ethanol,
using experimental data and data tables
• The use of the specific heat capacity of water to determine the approximate
amount of heat energy released in the combustion of fuel

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


2.1 Exothermic and endothermic
reactions
Chemical reactions occur when particles (atoms, molecules or ions) collide and are
rearranged to form new particles. Chemical reactions involve energy changes. As
the reactant particles are rearranged, the chemical energy of the reactants is also
‘rearranged’, although not in quite the same way.
In some chemical reactions, including the combustion of fuels, the
rearrangement of atoms causes energy to be released to the surroundings. For
example, the amount of energy released in the combustion of wood is large enough
to be easily seen or felt (Figure 2.1.1).
In other chemical reactions, energy is absorbed from the surroundings as the
chemical reaction takes place. The energy change in some reactions is very small
and can only be determined with specialised equipment.
In this section, you will learn about the energy changes that occur during
chemical reactions. You will also learn how to classify chemical reactions based on
their energy changes.

CHEMICAL ENERGY
FIGURE 2.1.1
There are many different forms of energy.You will be more familiar with some than
others. For example, you are in contact with forms of heat (thermal energy), light
(radiant energy), sound energy and electrical energy every day. You can probably
see, hear or feel some of them as you are reading these pages.
All substances have a form of energy called chemical energy. It is stored in the
bonds between atoms and molecules. This energy results from:
• attractions between electrons and protons in atoms
• repulsions between nuclei
• repulsions between electrons
• movement of electrons
• vibrations and rotations around bonds.
When you eat a meal, the bonds between the food molecules have stored energy
that you can access to provide energy for other chemical and physical activities that
take place in your body (Figure 2.1.2).

106

103 103

FIGURE 2.1.2 When you eat food, you access the chemical energy stored in the food. This energy
J kJ MJ
As you learned in Chapter 1, the SI unit for energy is the joule, J. Other units
× 10 3
× 10
3 also used for quantifying energy are kilojoules, kJ, and megajoules, MJ.
The relationship between joules and megajoules is:
1 J = 10–3 kJ = 10–6 MJ
× 106 This can also be expressed as:
FIGURE 2.1.3 1 MJ = 1000 kJ = 1 000 000 J
energy units.
Figure 2.1.3 shows how you can convert between different units of energy.
36 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
ENERGY CONSERVATION
According to the law of conservation of energy, energy cannot be created or
destroyed. However, it can change forms. When energy is transformed from one
form to another, the total amount of energy remains the same.
Systems and surroundings
When we talk about energy changes in chemical reactions, we often refer to a
system and its surroundings.
In chemistry, the system is usually the chemical reaction. When we say that
energy is released or absorbed by a system, we are referring to energy changes that
occur as bonds are broken and formed between the atoms of the elements involved
in the reaction.
The surroundings are usually regarded as everything else. For example, the
walls of a container in which a reaction takes place in the gas phase, or the water
in a solution in which a reaction takes place in the aqueous phase, can be regarded
as the surroundings for the reaction. Energy leaves the system (the reaction) and
enters the surroundings, or leaves the surroundings and enters the system.
Energy changes during chemical reactions
The reactants in a chemical reaction have a certain amount of chemical energy
stored in their bonds. The products that form as a result of the rearrangement of
particles during the chemical reaction have different bonds and so have a different
amount of chemical energy. Energy will be released or absorbed during the reaction
depending on the relative energies of the bonds within the reactants and products.
When fuels undergo combustion, they are able to release energy that can be used.
This is what makes them fuels.
Often the energy released to or absorbed from the surroundings is in the form of
heat (thermal energy). However, heat can be converted into other types of energy,
including light, electricity and movement (kinetic energy).

CHEMISTRY IN ACTION

Glow-in-the-dark light sticks


You might have seen glow-in-the-dark hoops, necklaces and bracelets similar to
those shown in Figure 2.1.4 at festivals or concerts, especially those held at night.
Glow-in-the-dark bracelets contain chemicals held in separate containers.
When these bracelets are bent, the containers break and the chemicals combine.
Light is produced through a process called chemiluminescence.
The chemistry of a glow stick is fairly straightforward. When the aqueous
reactants (hydrogen peroxide in one area and diphenyl oxalate in another area)
mix, energy is released from the reaction that occurs. This reaction is shown in
Figure 2.1.5.
O O

O C C O +HO 2 OH + 2CO2 + energy


2 2

diphenyl oxalate hydrogen hydroxybenzene


peroxide (phenol)
FIGURE 2.1.5
FIGURE 2.1.4
Instead of the energy from this reaction being released to the surroundings give off light that is the result of chemi-
luminescence.
solely as heat, a carrier molecule transfers the energy to a chemiluminescent dye
in the glow stick. The electrons in the dye are excited to higher energy levels. Light
is emitted as these electrons return to their original lower energy levels. The light
from the glow stick is simply the emission spectrum of the dye molecule.

CHAPTER 2 | ENERGY FROM FUELS 37


CHEMFILE
Glow-worms
Glow-worms (Figure 2.1.6) apply similar chemical principles to chemiluminescence
for their glow-in-the-dark bioluminescence. Three chemicals within the worm
combine. However, they require oxygen to produce light. When the worm breathes,
oxygen acts as the oxidising agent in the chemical reaction between the three
reactants producing the bioluminescence. Worms are able to control the amount of
‘glow’ by breathing in more or less oxygen.
FIGURE 2.1.6 A female glow-worm. The

EXOTHERMIC AND ENDOTHERMIC SYSTEMS


When the total chemical energy of the products of a chemical reaction is less than
the total chemical energy of the reactants, the excess energy is released to the
surroundings. Energy ‘exits’ the reaction system and the chemical reaction is called
an exothermic reaction.
The released energy can be shown in a chemical equation by writing ‘energy’ on
the product side of the arrow.
For example, the production of water from the reaction between hydrogen and
oxygen gas is an exothermic reaction. This can be represented by the equation:
2H2(g) + O2(g) → 2H2O(l) + energy
Another example of an exothermic reaction is the combustion of methane gas:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) + energy
Heat is given off to the surroundings. All combustion reactions give off heat
(energy) to the surroundings and are therefore exothermic reactions.
When the total chemical energy of the products of a chemical reaction is
greater than the total chemical energy of the reactants, energy is absorbed from the
surrounding environment. Energy ‘enters’ the reaction system and the chemical
reaction is called an endothermic reaction.
If an endothermic reaction takes place in a container, the container may feel
cold to the touch. This is because the reaction system is absorbing heat from the
surroundings, leaving the environment cooler.
In a chemical equation of an endothermic reaction, the energy that is required
can be written on the reactant side of the equation arrow.
For example, the decomposition of calcium carbonate is an endothermic
process. This can be represented by the equation:
If the total chemical energy of CaCO3(s) + energy → CaO(s) + CO2(g)
the products is less than the total
Endothermic reactions require the constant input of energy.
energy of the reactants, energy
will be released from the system Changes of state
into the surroundings. This is
called an exothermic reaction. Changes of state, such as a solid melting to form a liquid, are a type of physical
change, rather than a chemical change. These changes also involve energy being
If the total chemical energy of
absorbed or released.
the products is greater than the
total energy of the reactants, For example, the melting of ice into water requires the absorption of energy,
energy will be absorbed from the making it an endothermic process. The boiling of water to produce water vapour is
surroundings. This is called an also endothermic.
endothermic reaction. Conversely, condensing a gas to a liquid and freezing a liquid to form a solid
both release heat to the surroundings and so are exothermic processes.

38 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


CHEMFILE
Instant cold packs

FIGURE 2.1.7 An endothermic reaction

2.1 Review
SUMMARY

• Energy is measured in J, kJ or MJ: • A chemical reaction that releases energy to the


1 J = 10–3 –6
kJ = 10  MJ surroundings is called an exothermic reaction.
• Chemical energy is stored in the bonds between • A chemical reaction in which energy is absorbed
atoms and molecules. from the surroundings is called an endothermic
• Energy is conserved during a chemical reaction; reaction.
energy cannot be created or destroyed. • All combustion reactions are exothermic reactions.
• Chemical reactions and changes of state involve
energy changes.

KEY QUESTIONS

1 Which of the following statements about combustion reactions is correct?


A Combustion reactions are usually exothermic, meaning energy is
absorbed during the reaction.
B Combustion reactions are always exothermic, meaning energy is
absorbed during the reaction.
C Combustion reactions are usually endothermic, meaning energy is
absorbed by the system.
D Combustion reactions are always exothermic, meaning energy is released
during the reaction.
2 Convert the following energy values to kJ.
a 0.180 MJ
b 1.5 × 106 J
c 10.0 J
d 2.0 × 10–3 J
3 Explain the difference between the terms ‘system’ and ‘surroundings’ in
relation to a chemical reaction.
4 Explain the term ‘endothermic’ in relation to the total amount of chemical
energy of the reactants and products.

CHAPTER 2 | ENERGY FROM FUELS 39


2.2 Thermochemical equations and
energy profile diagrams
When fuels undergo combustion, energy is released in the form of heat. As you saw
in the previous section, the word ‘energy’ can be included in a combustion equation
to show that energy is released. However, it is generally more useful for a chemist to
be precise about the magnitude (size) of the energy change that takes place.
Thermochemical equations achieve this by including a sign and numerical
value for the energy change that occurs in the reaction.
It is also useful for chemists to be able to show the energy changes that occur as a
reaction proceeds. All reactions absorb some energy before they can proceed, even
if energy is released overall. An energy profile diagram represents the energy
changes that occur during the course of a reaction.
In this section, you will learn how to write and interpret thermochemical
equations and draw energy profile diagrams. Although the focus for this section
is on the combustion of fuels (which are exothermic reactions), you will also learn
about writing and representing other equations, including endothermic reactions.
These reactions are important for your understanding of some of the concepts that
will be covered in later chapters.

REPRESENTING ENERGY CHANGE IN A CHEMICAL


EQUATION
Enthalpy change
Enthalpy change is a measure of
the amount of energy absorbed or The chemical energy of a substance is sometimes called its heat content or
released during chemical reactions. enthalpy. It is given the symbol H. The enthalpy of the reactants in a chemical
H and is reaction is given the symbol Hr and the enthalpy of the products is given the
determined by subtracting the symbol Hp.
enthalpy of the reactants (Hr) from Most chemical processes take place in open systems under a constant pressure
Hp). (usually atmospheric). The exchange of heat energy between the system and its
surroundings under constant pressure is referred to as the enthalpy change,
or heat of reaction, and is given the symbol ∆H. The capital delta symbol (∆)
is commonly used in chemistry to represent ‘change in’. For example, ∆T is the
symbol for change in temperature.
reactants
energy Fuels provide you with energy by undergoing exothermic combustion reactions.
Energy

released
(ΔH negative)
Knowing the precise enthalpy change per mole or gram that occurs during
products combustion of different fuels helps you to decide which fuel might be most suitable
for a particular purpose.
Reaction progress For the general reaction:
reactants → products
the enthalpy change (∆H) is calculated by:
∆H = Hp – Hr

Enthalpy change in exothermic reactions


When Hp is less than Hr, energy is released from the system into the surroundings,
FIGURE 2.2.1 so the reaction is exothermic. The system has lost energy, so ∆H has a negative
value.
enthalpy of the products, so energy is released Therefore, for combustion reactions (which are exothermic reactions), ∆H < 0
(see Figure 2.2.1).

40 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Enthalpy change in endothermic reactions
When Hp is greater than Hr, energy must be absorbed from the surroundings, so
products
the reaction is endothermic. The system has gained energy, so ∆H has a positive

Energy
energy
value, i.e. ∆H > 0 (see Figure 2.2.2). absorbed
(ΔH positive)
Thermochemical equations reactants

The enthalpy change can be shown by writing the ∆H value to the right of the Reaction progress
chemical equation. Such an equation is called a thermochemical equation. The ∆H
value in a thermochemical equation usually has the units kJ mol–1. This means that
the amount of energy (in kJ) signified by the ∆H value corresponds to the mole
amounts specified by the coefficients in the equation.
For example, respiration in most living things can be considered as a type of
combustion reaction of glucose. Therefore, respiration is an exothermic reaction:
C6H12O6(aq) + 6O2(g) → 6CO2(g) + 6H2O(l) ∆H = –2803 kJ mol–1
FIGURE 2.2.2 For an endothermic reaction,
This thermochemical equation tells you that when 1 mole of glucose reacts with the enthalpy of the reactants is less than the
6 moles of oxygen to produce 6 moles of carbon dioxide and 6 moles of water,
2803 kJ of energy is released.
Enthalpy changes also occur during physical changes, so thermochemical
equations can be written for physical changes. Melting ice is an example of a
physical change. It is an endothermic process, because heat must be applied to
solid ice in order to convert it into liquid water. The thermochemical equation for
this reaction is:
H2O(s) → H2O(l) ∆H = +6 kJ mol–1
The ∆H value is positive because this is an endothermic reaction.

CHEMISTRY IN ACTION

Explosives—a blast of chemical energy


Humans have been using chemicals to make explosions
since 919 BCE. Chinese people first mixed saltpetre
(potassium nitrate), sulfur and charcoal with explosive
results. They quickly realised that there were many
uses for this mixture, which later became known as
gunpowder. It was put to military use and eventually led
to the development of bombs, cannons and guns.
Today, explosives are an essential tool for mining and
other engineering works, such as road construction,
tunnelling, building and demolition (see Figure 2.2.3).
Explosives transform chemical energy into large
quantities of thermal energy very quickly. Although thermal
energy is also released when fuels such as petrol and
natural gas burn, the rate of combustion in these reactions
is limited by the availability of oxygen gas to the fuel. In
contrast, the compounds making up an explosive contain
sufficient oxygen for a complete (or almost complete)
FIGURE 2.2.3
reaction to occur very quickly.

CHAPTER 2 | ENERGY FROM FUELS 41


CHEMISTRY IN ACTION

The chemistry behind an explosion


When chemical explosives, such as ammonium nitrate, Notice that 29 moles of gas (the total number of moles of
trinitrotoluene (TNT) and nitroglycerine decompose, they all products) are produced from 4 moles of nitroglycerine.
release large amounts of energy and gaseous products very The negative ∆H value indicates that this is an exothermic
quickly. reaction. At atmospheric pressure, the reactant products
This is the thermochemical equation for the decomposition would expand to fill a volume more than 10 000 times
of nitroglycerine: larger than the volume of the nitroglycerine! During a blast,
4C3H5N3O9(l) → 12CO2(g) + 10H2O(g) + 6N2(g) + O2(g) this gas is usually produced within a small hole into which
∆H = –1456 kJ mol–1 the explosive has been placed, creating huge pressures that
shatter the surrounding rock or structure.

THERMOCHEMICAL EQUATIONS AND MOLE RATIOS


The ∆H value in a thermochemical equation corresponds to the mole amounts
specified by the equation. If the coefficients in the equation are changed, the ∆H
value will also change.
For example, the thermochemical equation for the combustion of methanol can
be written as:
3
CH3OH(l) + O2(g) → CO2(g) + 2H2O(l) ∆H = –726 kJ mol–1
2
This means that 726 kJ of energy is released when 1 mole of methanol reacts
with 1.5 moles of oxygen gas, to produce 1 mole of carbon dioxide and 2 moles
of water.
If twice as much methanol were to react, then twice as much energy would be
released. So, if the coefficients of the equation are doubled, the ∆H value is also
doubled:
2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O(l) ∆H = –1452 kJ mol–1
If the mole amounts are tripled, the ∆H value is also tripled:
1
3CH3OH(l) + 4 O2(g) → 3CO2(g) + 6H2O(l) ∆H = –2178 kJ mol–1
2
The importance of states
It is very important to always include state symbols in thermochemical equations.
Physical changes involve an enthalpy change, so the state of the species in a chemical
reaction affects the enthalpy change of the reaction.
For example, both of the following equations represent physical changes
involving water. They have different ∆H values because the states are different.
H2O(s) → H2O(l) ∆H = +6.00 kJ mol–1
H2O(l) → H2O(g) ∆H = +40.7 kJ mol–1
You can see that it requires more energy to boil water than it does to melt ice.

H of reversing a chemical reaction


Reversing a chemical equation changes the sign but not the magnitude of ∆H.
For example, methane (CH4) reacts with oxygen gas to produce carbon dioxide
gas and water in an exothermic reaction:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = –890 kJ mol–1
If this reaction is reversed, the magnitude of ∆H remains the same because the
enthalpies of the individual chemicals have not changed, but the sign changes to
indicate that energy must be absorbed for this reaction to proceed.
CO2(g) + 2H2O(l) → CH4(g) + 2O2(g) ∆H = +890 kJ mol–1

42 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Worked example 2.2.1
CALCULATING ∆H FOR ANOTHER EQUATION

Iron reacts with oxygen according to the equation:


3Fe(s) + 2O2(g) → Fe3O4(s) ∆H = –1121 kJ mol–1
Calculate ∆H for the reaction represented by the equation:
2Fe3O4(s) → 6Fe(s) + 4O2(g)

Thinking Working
The reaction has been reversed in the ∆H for the second equation is positive.
second equation, so the sign for ∆H is
changed to the opposite sign.
Identify how the mole amounts in the The mole amount of Fe3O4 has
equation have changed. changed from 1 to 2, O2 has changed
from 2 to 4 and Fe has changed from
3 to 6. They have all doubled.
Identify how the magnitude of ∆H will The mole amounts of the chemicals
have changed for the second equation. have all doubled, so ∆H will also have
doubled.
Calculate the new magnitude of ∆H. 2 × 1121
(You will write the sign of ∆H in the = 2242
next step.)
Write ∆H for the second equation, ∆H = +2242 kJ mol–1
including the sign.

Worked example: Try yourself 2.2.1


CALCULATING ∆H FOR ANOTHER EQUATION

Carbon reacts with hydrogen according to the equation:


6C(s) + 3H2(g) → C6H6(g) ∆H = +49 kJ mol–1
Calculate ∆H for the reaction represented by the equation:
3C6H6(g) → 18C(s) + 9H2(g)

Activation energy
The energy required to break the bonds of reactants so that a reaction can proceed
is called the activation energy. The activation energy is an energy barrier that
must be overcome before a reaction can get started. (The concept of activation
energy is discussed in more detail in Chapter 7.)

An activation energy barrier exists for both exothermic and endothermic


reactions. If the activation energy for a reaction is very low, the chemical reaction
can be initiated as soon as the reactants come into contact because the reactants
already have sufficient energy for a reaction to take place. Special conditions are
not always required for reactions to occur. An example of this can be seen in the
reaction between zinc and hydrochloric acid on page 44.

CHAPTER 2 | ENERGY FROM FUELS 43


The reaction between zinc and hydrochloric acid produces hydrogen gas:
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2(g)
As you can see in Figure 2.2.4, bubbles of hydrogen gas are vigorously produced
as soon as zinc is added to the acid.

FIGURE 2.2.4 When zinc comes into contact with hydrochloric acid, it reacts almost immediately.

ENERGY PROFILE DIAGRAMS


The energy changes that occur during the course of a chemical reaction can be
shown on an energy profile diagram.
The energy profile diagram for an exothermic combustion reaction like the one
shown in Figure 2.2.5 indicates that the enthalpy of the products is always less
than the enthalpy of the reactants. Overall, energy is released and so the ∆H value
is negative. The energy profile also shows that, even in exothermic reactions, the
activation energy must first be absorbed to start the reaction.
The energy profile diagram for an endothermic reaction (Figure 2.2.6) shows
that the enthalpy of the products is greater than the enthalpy of the reactants.
Overall, energy is absorbed and so the ∆H value is positive. The energy profile also
shows the absorption of the activation energy before the release of energy as bonds
form in the products.
Energy absorbed
as bonds in
reactants break

activation
energy
reactants
Energy

activation
Energy

products energy
Energy released ΔH
as bonds form in
products ΔH
products
reactants

Reaction progress Reaction progress


FIGURE 2.2.5 The characteristic shape of FIGURE 2.2.6 The characteristic shape of an

reaction. reaction.

44 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


2.2 Review
SUMMARY

• Thermochemical equations include a ∆H value for • States of matter must be included in thermochemical
a chemical reaction. The unit of ∆H is usually equations because changes of state involve enthalpy
kJ mol–1. changes.
• The value of ∆H indicates the magnitude of the • Activation energy is the energy that must be
energy change and whether the energy is absorbed absorbed to break the bonds in the reactants so that
(a positive value) or released (a negative value). a chemical reaction can proceed. Both endothermic
• Reversing an equation causes the sign of ∆H to and exothermic reactions require activation energy.
change, as the reaction changes from exothermic • Energy profile diagrams show energy changes over
to endothermic, or vice versa. the course of a reaction. They show the relative
• Doubling the coefficients in a chemical reaction enthalpies of reactants and products and the
causes the ∆H value to also double, as twice as activation energy.
many reactants react to produce or absorb twice • Combustion reactions are always exothermic and
as much energy. so always have a negative ∆H value.

KEY QUESTIONS

1 Explain what a negative ∆H value indicates about a chemical reaction,


in terms of the relative enthalpies of the reactants and products.
2 When 1 mole of methane gas undergoes combustion in oxygen to produce
carbon dioxide and water, 890 kJ of energy is released. Write a balanced
thermochemical equation for this reaction.
3 The combustion of octane to form carbon dioxide and liquid water can be
written as:
1
C8H18(g) + 12 O2(g) → 8CO2(g) + 9H2O(l) ∆H = –5450 kJ mol–1
2
The combustion of octane to form carbon dioxide and steam can be
written as:
1
C8H18(g) + 12 O2(g) → 8CO2(g) + 9H2O(g)
2
How would the energy released by the combustion of 1 mole of octane to
form steam compare with the energy released by 1 mole of octane to form
Energy

liquid water?
4 The energy profile diagram in Figure 2.2.7 shows the energy changes during
the reaction of hydrogen and iodine to form hydrogen iodide:
H2(g) + I2(g) → 2HI(g)
a Is the reaction exothermic or endothermic?
b Describe the relative enthalpies of the reactants and products. Reaction progress
c Comment on the size of the activation energy compared with ∆H. FIGURE 2.2.7

5 The reaction for photosynthesis is the opposite to the reaction for respiration
shown on page 41. Write a thermochemical equation for photosynthesis.

CHAPTER 2 | ENERGY FROM FUELS 45


2.3 Energy from combustion

Review
The mole Mass
The mole is a unit used by chemists for counting particles. Chemists often use mass, measured in grams, to measure
One mole of any type of particle is a standard amount of an exact number of mole of an element or compound.
substance, which contains the same number of specified The molar mass of an element or compound is the mass
particles as there are atoms in exactly 12 g of carbon-12. of 1 mole of the element or compound. Molar mass is
The symbol for the amount of substance is n. The unit is derived from the relative atomic mass, relative molecular
mole, which is abbreviated to mol. mass or relative formula mass. A useful relationship links
Because atoms are very small, chemists have defined the amount of a substance (n), in mol, its molar mass (M),
the mole so that it represents a very large number. There in g mol–1, and the given mass of the substance (m), in g:
are 6.02 × 1023 particles in 1 mole. This number is called m
n=
M
Avogadro’s number and has the symbol NA.
Where needed, this relationship can be rearranged to:
A useful relationship links the amount of a substance (n), m
m = n × M or M =
in mol, Avogadro’s number (NA) and the number of n
particles in a substance (N):
N
n=N
A
Where needed, this relationship can be rearranged to:
N = n × NA

Fire heats our homes, powers our cars and entertains us with firework displays.
Bushfires can destroy homes and lives, devastating huge areas of bush and damaging
the habitat of many animals. However, a bushfire can also be an agent of regrowth
and renewal in land management.
Ancient cultures, such as the Ancient Greeks and Ancient Japanese, described
fire as one of the fundamental elements, along with air, earth and water (see
Figure 2.3.1).
Fire results from the combustion of substances. Combustion reactions need
three things:
• fuel to burn
• oxygen for the fuel to burn in
• energy to get the process started.
Fire can be understood and controlled by applying your knowledge of chemistry.
In this section, you will look at combustion reactions and their importance to
the world in more detail.

COMBUSTION AS A CHEMICAL PROCESS


Combustion reactions are exothermic reactions in which the reactant combines
FIGURE 2.3.1 According to the Ancient Greeks, with oxygen to produce oxides. This type of reaction is often referred to as an
oxidation reaction. The combustion of a hydrocarbon produces carbon dioxide
and water, provided there is enough oxygen present. An example is the combustion
of propane (C3H8), a major component of LPG (liquefied petroleum gas), shown
in the following equation:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆H = –2220 kJ mol–1
Note the following important features of this thermochemical equation.
• No atoms are created or destroyed in the reaction, so the numbers of atoms of
each element are balanced on the two sides of the equation.

46 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


• The balanced equation tells you the number of molecules of oxygen that are
required for the combustion of each molecule of propane.
• The enthalpy change for the reaction is negative, indicating that this is an
exothermic reaction.
• The enthalpy change is given in kJ mol–1. It tells you the energy released, in kJ,
according to the coefficients given in the equation.
• State symbols show the state of each reactant and product. (Although in a
combustion reaction, water is released as water vapour, the enthalpy change
of this thermochemical equation shows the energy change if liquid water is
formed.)

the addition of oxygen to form oxides, such as in a combustion reaction.

Complete and incomplete combustion


Combustion reactions can be described as complete or incomplete. The difference
between the two is due to the amount of oxygen available to react with the fuel.
Complete combustion occurs when oxygen is plentiful. The only products
are carbon dioxide and water.
An example is the complete combustion of methane:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
FIGURE 2.3.2
When the oxygen supply is limited, incomplete combustion occurs. As less
oxygen is available, not all of the carbon can be converted into carbon dioxide.
Carbon monoxide and/or carbon are produced instead. The hydrocarbon burns
with a yellow, smoky or sooty flame, due to the presence of glowing carbon particles.
Figure 2.3.2 shows the appearance of the different flames of a Bunsen burner due
to incomplete and complete combustion.
The equation for the incomplete combustion of methane to form carbon
monoxide is:
2CH4(g) + 3O2(g) → 2CO(g) + 4H2O(l)

CHEMFILE
Carbon monoxide poisoning

FIGURE 2.3.3

oxygen for the fuel to burn. The products of complete combustion are carbon
dioxide and water. When oxygen is not plentiful, incomplete combustion occurs.
The products of incomplete combustion are carbon monoxide and/or carbon

CHAPTER 2 | ENERGY FROM FUELS 47


WRITING EQUATIONS FOR COMPLETE COMBUSTION
OF FUELS
It is important to write chemical equations correctly because they tell you a lot
about chemical reactions. Writing equations for the complete combustion reactions
of fuels containing carbon and hydrogen is relatively straightforward, because the
products are always carbon dioxide and water.
Perhaps the most important of all combustion reactions involving fuels are those
that occur when petrol is burnt. Petrol is a mixture of hydrocarbons, including
octane.
The combustion reactions of octane (C8H18) and the other hydrocarbons in
petrol power the internal combustion engines in most of Australia’s 17.6 million
motor vehicles.

Worked example 2.3.1


WRITING EQUATIONS FOR COMPLETE COMBUSTION OF HYDROCARBON FUELS

Write the equation, including state symbols, for the complete combustion of
butane (C4H10).

Thinking Working
Add oxygen as a reactant and C4H10 + O2 → CO2 + H2O
carbon dioxide and water as
the products.
Balance carbon and hydrogen C4H10 + O2 → 4CO2 + 5H2O
atoms, based on the formula of
the hydrocarbon.
Find the total number of oxygen Total O
atoms on the product side. = (4 × 2) + 5
= 13
If this is an odd number, 2C4H10 + O2 → 8CO2 + 10H2O
multiply all of the coefficients in
the equation by two, except for
the coefficient of oxygen.
Balance oxygen by adding the 2C4H10 + 13O2 → 8CO2 + 10H2O
appropriate coefficient to the
reactant side of the equation.
Add state symbols. 2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l)

Worked example: Try yourself 2.3.1


WRITING EQUATIONS FOR COMPLETE COMBUSTION OF HYDROCARBON FUELS

Write the equation, including state symbols, for the complete combustion of
hexane (C6H14).

A similar series of steps can also be used to write the combustion equations for
other carbon-based fuels that contain oxygen; for example, alcohols.

48 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Worked example 2.3.2
WRITING EQUATIONS FOR COMBUSTION REACTIONS OF ALCOHOLS

Write the equation, including state symbols, for the complete combustion of
liquid ethanol (C2H5OH).

Thinking Working
Add oxygen as a reactant and C2H5OH + O2 → CO2 + H2O
carbon dioxide and water as
the products.
Balance carbon and hydrogen C2H5OH + O2 → 2CO2 + 3H2O
atoms, based on the formula of
the alcohol.
Find the total number of Total O on product side
oxygen atoms on the product = (2 × 2) + 3
side.
=7
Then subtract the one oxygen
Total O on product side – 1 in alcohol
atom in the alcohol molecule
from the total number = 7 – 1 = 6
of oxygen atoms on the
product side.
If this is an odd number, C2H5OH + O2 → 2CO2 + 3H2O
multiply all the coefficients
in the equation by two, except
for the coefficient of oxygen.
Balance oxygen by adding the C2H5OH + 3O2 → 2CO2 + 3H2O
appropriate coefficient to the
reactant side of the equation.
Add state symbols. C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g)

Worked example: Try yourself 2.3.2


WRITING EQUATIONS FOR COMBUSTION REACTIONS OF ALCOHOLS

Write the equation, including state symbols, for the complete combustion
of liquid methanol (CH3OH).

WRITING EQUATIONS FOR INCOMPLETE COMBUSTION


OF FUELS
When the supply of oxygen is insufficient, incomplete combustion of fuels occurs.
Equations can also be written to represent this. In general, for the incomplete
combustion of hydrocarbons, as well as carbon-based fuels that contain oxygen,
the products are carbon monoxide and/or carbon and water.

CHAPTER 2 | ENERGY FROM FUELS 49


Worked example 2.3.3
WRITING EQUATIONS FOR INCOMPLETE COMBUSTION OF FUELS

Write an equation, including state symbols, for the incomplete combustion


of ethane gas (C2H6) to form carbon monoxide and water vapour.

Thinking Working
Add oxygen as a reactant and carbon C2H6 + O2 → CO + H2O
monoxide and water as the products.
Balance the carbon and hydrogen C2H6 + O2 → 2CO + 3H2O
atoms, based on the formula of
the hydrocarbon.
Balance oxygen by adding the 5
C2H6 + O → 2CO + 3H2O
appropriate coefficient to the reactant 2 2
side of the equation.
If oxygen gas has a coefficient that is 2C2H6 + 5O2 → 4CO + 6H2O
half of a whole number, multiply all of
the coefficients in the equation by two.
Add state symbols. 2C2H6(g) + 5O2(g) → 4CO(g) + 6H2O(g)

Worked example: Try yourself 2.3.3


WRITING EQUATIONS FOR INCOMPLETE COMBUSTION OF FUELS

Write an equation, including state symbols, for the incomplete combustion


of liquid methanol (CH3OH) to form carbon monoxide and water vapour.

HEAT OF COMBUSTION
The heat of combustion of a fuel is defined as the enthalpy change that occurs
when a specified amount (e.g. 1  g, 1  L, 1  mol) of the fuel burns completely in
oxygen. It is usually measured at conditions of 298 K and 100 kPa, which means
that the water produced should be shown in the liquid state. The heat of combustion
can be given the symbol ∆Hc.

This means that the water produced should be shown in the liquid state.

Many fuels, including wood, coal and kerosene, are mixtures of chemicals and
do not have a specific chemical formula or molar mass. This means their heat of
combustion cannot be expressed in kJ mol-1. Therefore, it is measured only as
kJ g–1, kJ L–1 or MJ/tonne.

Only fuels that exist as pure substances can have their heat of combustion
–1
.

50 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


The heats of combustion for some common elements and compounds present
in fuels are listed in Table 2.3.1. Heat energy is released during combustion, so ∆Hc
always has a negative value.

TABLE 2.3.1

Substance Heat of combustion, ∆Hc (kJ mol–1)


Methane –890
Ethane –1560
Propane –2220
Butane –2886
Octane –5450
Methanol –725
Ethanol –1367
Hydrogen –286
Carbon (graphite) –394

As you learned in Chapter 1, when these fuels are burnt, not all the energy is
released as heat energy, and not all of the heat energy liberated can be harnessed
for a particular purpose, such as powering a vehicle or producing electricity.
However, even if the energy transformation process is not 100% efficient, you can
still use these values to compare the energy released from combustion of different
compounds.
As Worked Example 2.3.4 shows, you can use the data in Table 2.3.1 to calculate
the energy released on combustion of a specified mass of one of the fuels. The
energy released when n mol of a fuel burns is given by the equation:
Energy = n × ∆Hc

Worked example 2.3.4


CALCULATING ENERGY RELEASED BY A SPECIFIED MASS OF A PURE FUEL

Calculate the amount of energy released when 3.60 kg of butane (C4H10) is


burnt in an unlimited supply of oxygen.

Thinking Working
Calculate the number of m
n(C4H10) =
moles of the compound M
using: 3.60 × 103
m (in grams) =
n= 58.0
M = 62.1 mol
Multiply the number of moles Energy = n × ∆Hc
by the heat of combustion. = 62.1 × 2886
= 1.79 × 105 kJ

Worked example: Try yourself 2.3.4


CALCULATING ENERGY RELEASED BY A SPECIFIED MASS OF A PURE FUEL

Calculate the amount of energy released when 5.40 kg of propane (C3H8) is


burnt in an unlimited supply of oxygen.

CHAPTER 2 | ENERGY FROM FUELS 51


Energy content per gram
The energy content of a a fuel is often expressed in units of kilojoules per gram.
For a pure substance, the heat of combustion per gram can be calculated by
simply dividing the heat of combustion per mole (kJ mol–1) by the molar mass of
the substance.
For example, for ethanol (which is being burnt in a spirit burner in Figure 2.3.4):
Heat of combustion per mole = –1367 kJ mol–1
Molar mass = 46.0 g mol–1
–1367
Heat of combustion per gram = = –29.7 kJ g–1
46.0
For fuels that are mixtures, approximate values for the heat of combustion per
gram are shown in Table 2.3.2.

TABLE 2.3.2

Substance Heat of combustion (kJ g–1) (approx.)

Wood, dried –18

Peat, dried –25

Brown coal, dried –30

Black coal, dried –35

Energy content per tonne


FIGURE 2.3.4
The quantities of fuel consumed and the amount of energy produced are often
so large that the unit megajoules per tonnes, MJ/tonne, is a more useful way of
expressing the heat of combustion. For example, the Hazelwood power station
consumes about 13 million tonnes of coal in 1 year. It is more useful to consider the
energy released per tonne, rather than per gram of coal.
1 kJ = 10–3 MJ
1 g = 10–6 tonne
Therefore, 1 kJ g = 10  MJ/10–6 t.
–1 –3

This can be simplified to 1 kJ g–1 = 103 MJ/tonne.

EXTENSION

Energy density
Liquid fuels, such as petrol, are normally sold by volume rather than by mass.
For these fuels, it is often convenient to refer to the heat of combustion per
litre. Table 2.3.3 shows some heats of combustion per litre for common liquid
fuels. The energy released per litre of fuel is often called the fuel’s energy
density.

TABLE 2.3.3 Energy densities for some common liquid fuels

Substance Energy density (kJ L–1)

Petrol (unleaded 91) –34 200

Kerosene –36 500

Diesel fuel –38 000

Heating oil –38 500

Ethanol –23 400

52 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


2.3 Review
SUMMARY

• Combustion reactions are exothermic reactions that • Heats of combustion, ∆Hc, indicate the maximum
can be represented by balanced thermochemical amount of energy that can be released when a
equations. specified amount of fuel undergoes complete
• The products of the complete combustion of combustion. Common units are kJ mol–1, kJ g–1 and
hydrocarbons and carbon-based fuels containing MJ/tonne.
oxygen are carbon dioxide and water. • The amount of energy released by different fuels can
• Incomplete combustion, resulting in the production be compared by referring to heats of combustion.
of carbon monoxide and/or carbon, occurs when • For a pure fuel with a heat of combustion, ∆Hc,
hydrocarbons and carbon-based fuels containing measured in kJ mol–1, the energy released when
oxygen undergo combustion in a limited supply n mol of the fuel burns is given by the equation:
of oxygen. Energy = n × ∆Hc

KEY QUESTIONS

1 Write a balanced equation for the complete combustion of liquid benzene


(C6H6).
2 Information about two hydrocarbon fuels, propane and octane, is given in
Table 2.3.4.

TABLE 2.3.4

Characteristic Propane (C3H8) Octane (C8H18)


–1
Heat of combustion (kJ mol ) –2220 –5450
–1
Molar mass (g mol ) 44.0 114.0

Calculate the heat of combustion of each fuel in kJ g–1 and use your answer
to state which fuel produces more energy per kilogram.
3 Write a balanced equation for the incomplete combustion of ethanol
(C2H5OH) when carbon monoxide is formed.
4 Using the information in Tables 2.3.1 and 2.3.2, calculate the amount of
energy released when the following amounts of each fuel undergo complete
combustion.
a 250 g of methane
b 9.64 kg of propane
c 403 kg of ethanol
d 573 t of dried brown coal

CHAPTER 2 | ENERGY FROM FUELS 53


2.4 Determining the heat of
combustion of fuels
Knowing the energy released by similar quantities of different fuels helps you to
compare fuels and determine their suitability for specific purposes. For example,
the fuel used to power an aeroplane (Figure 2.4.1) is different from the fuel used
to power a car or bus.

FIGURE 2.4.1

In previous sections, you learned two ways of representing the energy change
for fuels involved in combustion reactions.
• The heat of combustion of a fuel gives the amount of energy released when a
specified amount of the fuel burns in oxygen.
• A thermochemical equation includes a ∆H value, which shows the amount of
heat released when a fuel undergoes combustion. The value of ∆H is based on
the stoichiometric ratios in the equation.
In this section, you will learn how knowledge of the specific heat capacity of
water can be used to obtain an experimental estimate of the energy released in the
combustion of a fuel.

SPECIFIC HEAT CAPACITY OF WATER


The specific heat capacity of a substance is a measure of the amount of energy
(usually in joules) needed to increase the temperature of a specific quantity of that
substance (usually 1 gram) by 1°C.
Specific heat capacity is given the symbol C and is usually expressed in joules
per gram per degrees Celsius, i.e. J g–1 °C–1. It can also be expressed in joules per
grams per kelvin, i.e. J g–1 K–1 (an increase of 1°C is the same as an increase of 1 K).

54 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


The specific heat capacities of some common substances are listed in Table
2.4.1. You can see that the value for water is relatively high.

TABLE 2.4.1

Substance Specific heat capacity


(J g–1 °C–1)

Water 4.18

Glycerine 2.43

Ethanol 2.46

Sand 0.48

Copper 0.39

Lead 0.16

The specific heat capacity of a substance is a reflection of the types of bonds


holding the molecules, ions or atoms together in the substance.
Water has a specific heat capacity of 4.18 J g–1 °C–1. This means that a substance is the amount of
energy required to increase
4.18 joules of heat energy are needed to increase the temperature of 1 gram of
water by 1°C. This relatively high value is due to the hydrogen bonds between
the water molecules. The higher the specific heat capacity, the more effectively a
capacity is frequently written
material stores heat energy. –1
°C–1.
When a substance is being heated, its temperature rises. The temperature of
1  g of water increases by 1°C when it is supplied with 4.18 J of heat energy. In
comparison, 2.43 J of heat energy is required to increase the temperature of 1 g of 80
glycerine by 1°C. The effect of the different specific heat capacities of water and
70
glycerine on their temperatures when heated can be seen in Figure 2.4.2.
60

T (°C)
50
Water is distinguished by its very high heat capacity, which is a consequence of glycerine
40
the hydrogen bonding between its molecules. The special properties of water are
30 water
described in .
20

10 20 30 40 50 60 70 80 90 100
q (kJ)
The specific heat capacity of water can be used to calculate the heat energy in joules
FIGURE 2.4.2 A comparison of the effect of the
needed to increase the temperature of a given mass of water by a particular amount.
Heat energy is given the symbol q. glycerine on the increase in temperature (T).
A useful equation can be written: Water has a very high heat capacity so it
Heat energy = specific heat capacity × mass × temperature change requires more heat energy (q) to increase its
Using symbols, the equation can be written as:
q = C × m × ∆T
where q is the amount of heat energy (in J), C is the specific heat capacity
(in J g–1 °C–1), m is the mass (in g) and ∆T is the temperature change (in °C).

The heat energy required to increase the temperature of a given mass of water

q=C×m T
where q C
–1
°C–1), m T is the temperature change (in °C).

CHAPTER 2 | ENERGY FROM FUELS 55


Worked example 2.4.1
CALCULATING THE AMOUNT OF ENERGY REQUIRED TO HEAT A SPECIFIED
MASS OF WATER USING SPECIFIC HEAT CAPACITY

Calculate the heat energy, in kJ, needed to increase the temperature of 500 mL
of water by 15°C.

Thinking Working
Change the volume of water, in mL, 1 mL of water has a mass of 1 g, so
to mass of water, in g. Remember that 500 mL of water has a mass of 500 g.
1 mL of water has a mass of 1 g.
Find the specific heat capacity of The specific heat capacity of water is
water from the data in Table 2.4.1. 4.18 J g–1 °C–1.
To calculate the quantity of heat q = 4.18 × 500 × 15
energy in joules, use the formula: = 3.14 × 104 J
–1 –1
q = C (J g °C ) × m (g) × ∆T (°C)
Express the quantity of energy in kJ. q = 3.14 × 104 × 10–3
Remember that to convert from J to = 31.4 kJ
kJ, you multiply by 10–3.

Worked example: Try yourself 2.4.1


CALCULATING THE AMOUNT OF ENERGY REQUIRED TO HEAT A SPECIFIED
MASS OF WATER USING SPECIFIC HEAT CAPACITY

Calculate the heat energy, in kJ, needed to increase the temperature of 375 mL
of water by 45°C.

EXPERIMENTAL DETERMINATION OF HEAT OF COMBUSTION


When a combustion reaction takes place, chemical energy is converted to thermal
energy. You can use the thermal energy released by a specific quantity of fuel as
it undergoes combustion to heat a measured volume of water. If you measure the
temperature change of the water, it can be used to determine the approximate
amount of energy released by the fuel.
An experimental arrangement for estimating the heat of combustion of a liquid fuel,
such as ethanol, is shown in Figure 2.4.3.

56 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


clamp

thermometer
bosshead
metal loop stirrer
metal can containing
retort stand
measured volume
of water

water

heatproof mat
spirit burner
containing ethanol

FIGURE 2.4.3

Figure 2.4.4 summarises the steps followed in this experiment.

Measure a volume
After some time,
of water, e.g. Measure the mass of
Light the burner and extinguish the
100 mL, and place it Measure the mass burner and record the burner and
heat the water,
in the metal can. of the spirit burner the highest remaining fuel. Hence
stirring
Measure the initial and fuel. temperature reached deduce the mass of
continuously.
temperature of the by the water. fuel consumed.
water.

FIGURE 2.4.4

Three key pieces of information collected from this procedure are the:


• mass of water (because the density of water is 1.00 g mL–1, the volume of water,
measured in mL, is equal to its mass, in g)
• change in temperature of the water, ∆T
• mass of fuel consumed, m.
This data can be used to determine the heat of combustion of the fuel, as shown
in Worked Example 2.4.2.
Note that when performing these calculations, it is assumed that all of the energy
released by the combustion of the fuel is used to heat the water. In reality, some of
the energy heats the metal can as well as being lost to the surroundings.
For this reason, measurements of heats of combustion from these experiments
only give approximate values. More accurate measurements are obtained using
bomb calorimetry, which is discussed in Chapter 17.

Worked example 2.4.2


CALCULATING THE HEAT OF COMBUSTION OF A FUEL FROM EXPERIMENTAL DATA

0.355 g of methanol (CH3OH) undergoes complete combustion in a


spirit burner. The heat energy released is used to heat 100 mL of water.
The temperature of the water rose from 20.24°C to 37.65°C. Calculate the
heat of combustion of methanol in kJ mol–1.

CHAPTER 2 | ENERGY FROM FUELS 57


Thinking Working
Calculate the temperature change of ∆T = 37.65 – 20.24
the water. = 17.41°C
Use the specific heat capacity of water q = 4.18 × 100 × 17.41
to determine the energy used to heat = 7277 J
the water. Use the formula:
q = C × m × ∆T
(m in this formula is the mass of water.)
Express the quantity of energy in kJ. q = 7277 × 10–3
Remember that to convert from J to kJ, = 7.277 kJ
you multiply by 10–3.
Calculate the amount, in moles, of 0.355
n=
methanol using the formula: 32.0
m = 0.0111 mol
n=
M
Determine the heat of combustion of –7.277
Heat of combustion =
methanol, in kJ mol–1. 0.0111
Heat of combustion = = –656 kJ mol–1
heat energy released by sample (Note: The negative sign indicates the
amount of sample (in mol) reaction released energy, causing the
temperature to rise.)

Worked example: Try yourself 2.4.2


CALCULATING THE HEAT OF COMBUSTION OF A FUEL FROM
EXPERIMENTAL DATA

0.295 g of ethanol (C2H5OH) undergoes complete combustion in a spirit burner.


The heat energy released is used to heat 100 mL of water. The temperature of
the water rose from 19.56°C to 38.85°C. Calculate the heat of combustion of
ethanol in kJ mol–1.

DETERMINING THE ∆H VALUE FOR THERMOCHEMICAL


EQUATIONS
Experimentally determined heats of combustion for different elements and
compounds used as fuels can be listed in a data table, such as that shown in
Table 2.4.2.

TABLE 2.4.2

Fuel Heat of combustion, ∆Hc (kJ mol–1)


Octane –5450
Butane –2886
Propane –2220
Ethane –1560
Ethanol –1367
Methane –890
Methanol –725
Carbon (graphite) –394
Hydrogen –286

58 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


This data can be used to write thermochemical equations for the combustion of
these fuels. For example, the equation for the complete combustion of propane is:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆H = –2220 kJ mol–1
In this equation, the coefficient of propane is 1 so the ∆H value is the same as
the heat of combustion.
If the coefficient of the fuel in the combustion equation is 2 or more, the heat
of combustion must be multiplied by this number to determine ∆H. For example,
the thermochemical equation for the complete combustion of butane is written as:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l) ∆H = –5772 kJ mol–1
∆H in this case is twice the heat of combustion, 2 × –2886 = –5772 kJ mol–1.
Note that heats of combustion measured in kJ g–1 should be converted to units
of kJ mol–1 for use in thermochemical equations. Combustion reactions are always
exothermic, so the enthalpy change always has a negative sign.

Worked example 2.4.3


WRITING A THERMOCHEMICAL EQUATION USING HEAT OF COMBUSTION DATA

Write a thermochemical equation for the complete combustion of octane (C8H18).

Thinking Working
Add oxygen as a reactant and C8H18 + O2 → CO2 + H2O
carbon dioxide and water as the
products in the equation.
Balance the carbon, hydrogen 2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(l)
then oxygen atoms.
Add states.
Obtain the heat of combustion, The heat of combustion of octane is
in kJ mol–1, from Table 2.4.2. –5450 kJ mol–1.
Determine ∆H for the ∆H = 2 × –5450 = –10 900 kJ mol–1
thermochemical equation
by multiplying the heat of
combustion by the coefficient
of the fuel in the balanced
equation.
Write the thermochemical 2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(l)
equation. ∆H = –10 900 kJ mol–1

Worked example: Try yourself 2.4.3


WRITING A THERMOCHEMICAL EQUATION USING HEAT OF COMBUSTION DATA

Write a thermochemical equation for the complete combustion of ethane (C2H6).

CHAPTER 2 | ENERGY FROM FUELS 59


2.4 Review
SUMMARY

• The specific heat capacity of a substance measures • Heat of combustion is the energy released when a
the quantity of energy (usually in joules) needed to specified quantity of a substance (usually 1 mole,
increase the temperature of a specified quantity of 1 gram or 1 litre) is burnt.
that substance (usually 1 gram) by 1°C. • The specific heat capacity of water can be used in
• The specific heat capacity of water is 4.18 J g–1 °C–1. the experimental determination of the approximate
• The heat energy required to increase the amount of heat energy released in the combustion
temperature of a given mass of water by a particular of a fuel.
amount can be calculated using the equation: • Heat of combustion data can be used to determine
q = C × m × ∆T the enthalpy change, ∆H, in a thermochemical
where q is heat energy (in J), C is the specific heat equation.
capacity (in J g–1 °C–1), m is mass (in g) and ∆T is
the temperature change (in °C).

KEY QUESTIONS

1 Calculate the heat energy, in kJ, needed to increase the temperature of


1.00 kg of water by 25.0°C.
2 What assumptions are made when making calculations relating to the heat
of combustion of fuels using experimental data obtained from the apparatus
shown in Figure 2.4.3 (on page 57)?
3 A temperature rise of 1.78°C was observed when 1.00 × 10–3 mol of
propane gas was burnt and used to heat 300 mL of water. Calculate the
heat of combustion for propane in kJ mol–1, assuming all the heat released
was used to heat the water.
4 A temperature rise of 11.5°C was observed when 0.500 g of butane gas
(C4H10) was burnt and used to heat 500 mL of water. Calculate the heat of
combustion, in kJ g–1, for butane, assuming all the heat released is used to
heat the water.
5 The heat of combustion of methane is –890 kJ mol–1.
a Write a thermochemical equation for the complete combustion
of methane.
b Determine the mass of methane, in g, which has to be burnt in order
to heat 500 mL of water from 20.0°C to boiling. Assume all the heat
released was used to heat the water.

60 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Chapter review
KEY TERMS

activation energy endothermic heat of combustion


bioluminescence energy density incomplete combustion
chemical energy energy profile diagram law of conservation
chemiluminescence enthalpy of energy surroundings
chemiluminescent enthalpy change oxidation system
complete combustion exothermic SI units thermochemical equation
decomposition heat content specific heat capacity volume

Exothermic and endothermic reactions c Reactions that release energy overall do not need
1 Convert the following units of energy to the unit given to absorb activation energy.
(to 3 significant figures). d The match used to light a fire is providing activation
a 2205 J to kJ energy.
b 0.152 kJ to J 6 The combustion reaction of ethyne gas that occurs
c 1 890 000 J to MJ in a welding machine can be represented by the
d 0.0125 MJ to kJ thermochemical equation:
2 Decide whether the following processes are 2C2H2(g) + 5O2(g) → 4CO2(g) + 2H2O(l)
exothermic or endothermic. Give reasons for your ∆H = –2619 kJ mol–1
answers. a Is this reaction endothermic or exothermic?
a burning of wood b What would be the new value of ∆H if the equation
b melting of ice was now written as follows?
c recharging of a car battery 4C2H2(g) + 10O2(g) → 8CO2(g) + 4H2O(l)
d decomposition of plants in a compost heap 7 Explain why reversing a chemical reaction reverses
the sign of ∆H.
3 What is the difference between ‘bioluminescence’
and ‘chemiluminescence’? Give an example in your 8 The combustion of butane gas in portable stoves can
answer. be represented by the thermochemical equation:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l)
Thermochemical equations and energy profile ∆H = –5772 kJ mol–1
diagrams a How does the overall energy of the bonds in the
4 Which one of the following is correct about the energy reactants compare with the overall energy of the
profile diagrams of both endothermic and exothermic bonds in the products?
reactions? b Draw an energy profile diagram for the reaction,
A There is always less energy absorbed than released. labelling ∆H and activation energy.
B The enthalpy of the products is always less than the
energy of the reactants. Energy from combustion
C Some energy is always absorbed to break bonds in 9 Write a balanced equation for the complete
the reactants. combustion of butanol (C4H9OH), a commonly
D The ∆H value is the difference between the enthalpy used biofuel.
of the reactants and the highest energy point 10 Write a balanced equation for the incomplete
reached on the energy profile. combustion of butane (C4H10) where carbon monoxide
5 Identify whether each of the following statements is formed.
related to activation energy is true or false. 11 Calculate the energy released when 5.00 kg of
a Activation energy is the energy required to break methane (CH4) is burnt in an unlimited supply
bonds in the reactants. of oxygen. The heat of combustion of methane is
b Reactions that start immediately do not have an –890 kJ mol–1. (Give your answer in megajoules, MJ.)
activation energy.

CHAPTER 2 | ENERGY FROM FUELS 61


12 a Use the data from Table 2.3.1 on page 51 to Connecting the main ideas
calculate the energy available from 1 kg of each of 17 In a steelworks, carbon monoxide present in the
the following fuels. exhaust gases of the blast furnace can be used as
i Octane a fuel elsewhere in the plant. It reacts according to
ii Butane the equation:
iii Hydrogen 1
CO(g) + O2(g) → CO2(g) ∆H = –283 kJ mol–1
b Use the results of your calculations in part a to 2
list octane, butane and hydrogen in order of most a Which has the greater total enthalpy: 1 mol of
energy produced per kilogram to least energy CO(g) and 0.5 mol of O2(g) or 1 mol of CO2(g)?
produced per kilogram. b Write the value of ∆H for the following equations:
i 2CO(g) + O2(g) → 2CO2(g)
Determining the heat of combustion of fuels
ii 2CO2(g) → 2CO(g) + O2(g)
13 Calculate the energy needed to heat:
18 A temperature rise of 5.52°C was observed when
a 100 mL of water from 20.0°C to 80.0°C
0.0450 g of ethane (C2H6) was burnt and used to heat
b 250 mL of water from 25.0°C to 100.0°C 100.0 mL of water. Use this information to write a
c 1.5 kg of water from 20.0°C to 30.0°C balanced thermochemical equation for the complete
d 2300 g of water from 18.0°C to 100.0°C combustion of ethane.
e 300 g of cooking oil from 18.0°C to 100.0°C 19 A 500 mL volume of water in a beaker was heated
(C(cooking oil) = 2.2 J g–1 °C–1). using the energy released by the combustion of a
14 A 200 mL beaker of water at a temperature of 3.00 g piece of wood. The observed temperature rise
21.0°C is heated with 10.0 kJ of energy. Calculate the was 22.9°C.
temperature reached by the beaker of water. a Calculate the heat of combustion of wood in kJ g–1
15 0.254 g of black coal was burnt and used to heat and in MJ/tonne.
300 mL of water. The temperature of the water b Would the heat of combustion you calculated in
rose from 18.25°C to 24.92°C. Calculate the heat of part a be higher or lower than the actual heat of
combustion, in kJ g–1, of the coal. Assume all of the combustion of the wood. Give reasons for your
heat released during combustion was used to heat answer.
the water.
16 The heat of combustion of hydrogen is –286 kJ mol–1.
Write a thermochemical equation for the complete
combustion of hydrogen.

62 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


CHAPTER

Stoichiometry and the


combustion of fuels
When fuels undergo combustion, they produce gases, such as carbon dioxide and
water vapour, and release energy. The energy released by the combustion of fuels
is used every day for electricity, heating, cooking and transport.
While humans depend on the energy released by combustion, the gases that are
also released can have significant environmental impacts. Both carbon dioxide and
water vapour are greenhouses gases, capable of absorbing radiation from the Sun
and re-emitting radiation in the infrared region of the electromagnetic spectrum.
In order to be able to explain the chemical process of combustion, it is important
that you understand the nature of gases. In this chapter, you will explore the
properties of gases and relate these to the kinetic molecular theory. You will learn
how the pressure and volume of a gas sample are measured and how the volume
of a gas can be calculated from its amount, measured in moles. You will also
learn how to perform stoichiometric calculations relating to gases and the energy
produced during the combustion of fuels.

Key knowledge
• The definition of gas pressure including units, the universal gas equation and
standard laboratory conditions (SLC) at 25°C and 100 kPa
• Calculations related to the combustion of fuels including use of mass–mass,
mass–volume and volume–volume stoichiometry in calculations of enthalpy
change (excluding solution stoichiometry) to determine heat energy released,
reactant and product amounts and net volume of greenhouse gases at a given
temperature and pressure (or net mass) released per MJ of energy obtained

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


3.1 Introducing gases
Whenever fuels undergo combustion, one or more gases are produced. Therefore,
it is essential that you understand the nature of gases and their properties to gain a
full appreciation of the process of combustion.
Every day you observe the behaviour of gases. Examples are shown in Figure
3.1.1. Such examples tell you a great deal about the physical properties of gases—
those properties that can be observed and measured without changing the nature
of the gas itself.
In this section, you will learn about the properties and behaviour of gases.

(a) (b)

(c)

FIGURE 3.1.1

64 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


PROPERTIES OF GASES
Each of the examples shown in Figure 3.1.1 can be explained in terms of the
properties of gases. Table 3.1.1 summarises some of the properties of gases and
compares them with the properties of solids and liquids. These observations can be
used to develop a particle model of gas behaviour.

TABLE 3.1.1

Gases Liquids Solids

Density Low High High

Volume and Fill the space Fixed volume, adopt Fixed volume and
shape available, because shape of container, shape, because
particles move because particles are particles are affected
independently of affected by attractive by attractive forces
one another forces

Compressibility Compress easily Almost Almost


incompressible incompressible

Ability to mix Gases mix together Liquids mix together Solids do not mix
rapidly slowly unless stirred unless finely divided

The low density of gases, relative to that of liquids and solids, suggests that
the particles in a gas are much more widely spaced apart. The mass of any gas in
a given volume is less than the mass of a liquid or solid in the same volume. The
observation that gases are easily compressed can also be explained if gas particles
are widely spaced.
The fact that gases spread to fill the space available, as shown in Figure 3.1.2,
suggests that the particles of a gas move independently of each other.
The wide spacing and independent movement of particles explains why different
gases mix rapidly.

Water takes the shape of a container, A gas takes up the shape and volume
but its volume remains constant. of a container.

FIGURE 3.1.2

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 65


KINETIC MOLECULAR THEORY
Scientists have developed a model to explain gas behaviour based on the behaviour
of the particles of a gas. This model is known as the kinetic molecular theory of
gases. According to this theory:
• gases are composed of small particles, either atoms or molecules
• the volume of the particles in a gas is very small compared with the volume they
occupy. Consequently, most of the volume occupied by a gas is empty space
• gas particles move rapidly in random, straight-line motion
• particles collide with each other and with the walls of the container
• the forces between particles are extremely weak
• kinetic energy (KE) is the energy of motion. The kinetic energy of a particle is
calculated from the formula:
1
KE = mv2
2
where KE is in joules, mass (m) is in grams, and velocity (v) is in metres
per second.
In a gas, when particles collide, the kinetic energy of the gas particles can be
transferred from one particle to another, but the total kinetic energy remains
constant. Therefore, collisions between gas particles are described as elastic
collisions—kinetic energy is conserved.
• The average kinetic energy of the particles increases as the temperature of the
gas increases.

THE NATURE OF PRESSURE AND VOLUME


When you blow up a balloon, the balloon expands because you put more air into
it and the rubber of the balloon stretches. If you then plunge that balloon into
liquid nitrogen, as shown in Figure 3.1.3, the balloon shrinks dramatically. The
temperature of the gas decreases, causing the volume to decrease. Pumping more
air into a tyre, as shown in Figure 3.1.4, increases the pressure inside the tyre.
In section 3.2, you will examine the mathematical relationship between amount
(number of moles), volume, pressure and temperature of a gas. This requires an
understanding of the nature of volume and pressure.

FIGURE 3.1.3

66 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


FIGURE 3.1.4

Volume
Volume is the quantity used to describe the space that a substance occupies. Because
a gas occupies the whole container that it is in, the volume of a gas is equal to the
volume of its container.
a = 10 cm a = 1 cm

a a
a

a
a

1000 cm3 = 1 L 1 cm3 = 1 mL

FIGURE 3.1.5

There are several different units used for volume, some of which are represented
in Figure 3.1.5. The common units are litre (L), millilitre (mL), cubic metre
(m3) and cubic centimetre (cm3). Small volumes of gas are usually measured in
millilitres (mL) or litres (L). Very large samples are measured in cubic metres (m3).
• 1 mL = 1 cm × 1 cm × 1 cm = 1 cm3
• 1 L = 1 × 103 mL or 1000 mL
• 1 m3 = 1 m × 1 m × 1 m = 100 cm × 100 cm × 100 cm = 1 × 106 cm3
• 1 m3 = 1 × 106 cm3 = 1 × 106 mL = 1000 L

Worked example 3.1.1


CONVERTING VOLUME UNITS
A gas has a volume of 255 mL.

What is its volume in:


a cubic centimetres (cm3)?
b litres (L)?
c cubic metres (m3)?

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 67


Thinking Working

Recall the conversion a The units of mL and cm3 are equivalent.


factors for each of the 1 mL = 1 cm3
units of volume. Apply
255 mL = 255 cm3
the correct conversion to
each situation. b 1000 mL = 1 L
Divide volume in mL by 1000 to convert to L.
255
255 mL =
1000
= 0.255 L
c 1 × 106 mL = 1 m3
Divide volume in mL by 1 × 106 to convert to m3.
255
255 mL =
1 × 106
= 2.55 × 10–4 m3

Worked example: Try yourself 3.1.1


CONVERTING VOLUME UNITS
A gas has a volume of 700 mL.

What is its volume in:


a cubic centimetres (cm3)?
b litres (L)?
c cubic metres (m3)?

Pressure
People often talk about exerting pressure on something as if it is some kind of force.
In terms of the kinetic theory of gases, pressure is defined as the force exerted on a
unit area of a surface by the particles of a gas as they collide with the surface.
The more a gas is compressed, the more frequently the gas particles collide with
each other and the walls of their container. The increased frequency of collisions
with the walls of the container increases the force on the walls of the container, such
as the inside of a tyre. The force per unit area is described as pressure.
Air is a mixture of gases including nitrogen, oxygen, carbon dioxide and argon.
In air, the nitrogen molecules collide with the walls of a container, exerting a
pressure. In a similar way, the oxygen molecules exert a pressure, as do molecules
of each gas present in the mixture. In the gaseous mixture of nitrogen and oxygen
shown in Figure 3.1.6, the measured pressure is the sum of the partial pressure
of oxygen and the partial pressure of nitrogen.

Oxygen (O2) Nitrogen (N2) Mixture of nitrogen and oxygen


Pressure = 20 kPa Pressure = 80 kPa Pressure = (80 + 20) kPa
Temperature = 20°C Temperature = 20°C = 100 kPa
Temperature = 20°C

FIGURE 3.1.6

68 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Units of pressure
CHEMFILE
Because pressure is the force exerted on a unit area of a surface, the relationship
can be written as: Torricelli’s barometer
force In the 17th century, the Italian physicist
Pressure =
area Evangelista Torricelli invented the
F earliest barometer, an instrument used
P=
A to measure atmospheric pressure.
The units of pressure depend on the units used to measure force and area. Over
the years, scientists in different countries have used different units to measure force one end, containing mercury. The tube
and area, so there are a number of different units of pressure.
The SI unit for force is the newton (N) and the SI unit for area is the square metre
(m2). Therefore, the SI units of pressure are newtons per square metre (N m–2). as seen in Figure 3.1.7.
One newton per square metre is equivalent to a pressure of one pascal (Pa).
In 1982, the International Union of Pure and Applied Chemistry (IUPAC), the
organisation responsible for naming chemicals and setting standards, adopted a
standard for pressure equivalent to 100 000 Pa or 100 kPa. This gave rise to a new
pressure unit, the bar, where 1 bar equals 100 kPa.
The use of mercury barometers resulted in pressure often being measured in
millimetres of mercury, or mmHg.
Another unit for pressure is the standard atmosphere (atm). One standard
atmosphere (1 atm) is the pressure required to support 760 millimetres of mercury
(760 mmHg) in a mercury barometer at 25°C. This is the average atmospheric took his barometer to higher altitudes
pressure at sea level. One atmosphere equals 101.3 kPa.
Summary of pressure units
There are four common units of gas pressure: pascal, bar, millimetres of mercury
and atmosphere (Table 3.1.2).

TABLE 3.1.2

Name of unit Symbol for unit Conversion to N m–2


vacuum
newtons per square metre N m–2

pascal Pa 1 Pa = 1 N m–2

kilopascal kPa 1 kPa = 1 × 103 Pa = 1 × 103 N m–2 h = 760 mm


atmosphere atm 1 atm = 101.3 kPa = 1.013 × 105 N m–2 for standard
atmosphere mercury
bar bar 1 bar = 100 kPa = 1.00 × 105 N m–2

millimetres of mercury mmHg 760 mmHg = 1 atm = 1.013 × 105 N m–2 atmospheric
pressure

1 bar = 100 kPa = 1.00 × 105 N m–2


1 atm = 101.3 kPa = 1.013 × 105 N m–2

FIGURE 3.1.7
These relationships can be used to convert pressure from one unit to another.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 69


Worked example 3.1.2
CONVERTING PRESSURE UNITS
Mount Everest is the highest mountain on Earth.

a The atmospheric pressure at the top of Mount Everest is 0.337 bar.


What is the pressure in kilopascals (kPa)?
b The atmospheric pressure at the top of Mount Everest is 253 mmHg.
What is the pressure in atmospheres (atm)?
c The atmospheric pressure at the top of Mount Everest is 0.333 atm.
What is the pressure in kilopascals (kPa)?
d The atmospheric pressure at the top of Mount Everest is 253 mmHg.
What is the pressure in bars?

Thinking Working
a To convert bars to kilopascals, use the 0.337 bar = 0.337 × 100
conversion relationship: = 33.7 kPa
1 bar = 100 kPa
To change bar to kPa, multiply the value
by 100.
b To convert millimetres of mercury to 253
253 mmHg =
atmospheres, use the relationship: 760
1 atm = 760 mmHg = 0.333 atm
To change mmHg to atm, divide the value
by 760.
c To convert atmospheres to kilopascals, use the 0.333 atm = 0.333 × 101.3
conversion relationship: = 33.7 kPa
1 atm = 101.3 kPa
To change atm to kPa, multiply the value by
101.3.
d This can be done in two steps. First, convert 253
253 mmHg =
millimetres of mercury to atmospheres. Use 760
the conversion relationship: 253
253 mmHg = × 1.013
760 mmHg = 1 atm 760
To change mmHg to atm, divide the value by = 0.337 bar
760. Keep the answer in your calculator and
proceed to the next step.
Next, convert atmospheres to bar. Use the
conversion relationship:
1 atm = 1.013 bar
To change atm to bar, multiply the quotient
from the previous step by 1.013.

Worked example: Try yourself 3.1.2


CONVERTING PRESSURE UNITS
Cyclone Yasi was one of the biggest cyclones in Australian history.

a The atmospheric pressure in the eye of Cyclone Yasi was measured as


0.902 bar. What was the pressure in kilopascals (kPa)?
b What was the pressure in the eye of Cyclone Yasi in atmospheres (atm)
if it is known to be 677 mmHg?
c If the atmospheric pressure in the eye of Cyclone Yasi was 0.891 atm,
what was the pressure in kilopascals (kPa)?
d The atmospheric pressure in the eye of Cyclone Yasi was 677 mmHg.
What was the pressure in bars?

70 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


3.1 Review
SUMMARY

• One or more gases are produced whenever a fuel • To convert between different volume units, use
undergoes combustion. these relationships:
• Gas properties can be explained by the kinetic 1 L = 1000 mL = 1000 cm3
molecular theory. 1 m3 = 1 × 106 cm3 = 1 × 106 mL = 1000 L
• According to the kinetic molecular theory: • Pressure is defined as the force per unit area.
– the volume of the particles in a gas is very small • The pressure exerted by a gas depends on the
compared with the distance between the particles collisions of gas particles against the wall of
– the average kinetic energy of the particles in a gas the container.
is proportional to its temperature • To convert between different pressure units, use
– gas particles are in rapid random motion, these relationships:
colliding with each other and the container wall 1 bar = 100 kPa = 1.00 × 105 Pa
– the forces between particles in a sample of gas 1 atm = 760 mmHg = 1.013 × 105 Pa
are negligible. = 101.3 kPa = 1.013 bar

KEY QUESTIONS

1 Use the kinetic molecular theory to explain the following observed properties
of gases.
a Gases occupy all the available space in a container.
b Gases can be easily compressed compared with their corresponding
liquid forms.
c A given volume of a gaseous substance weighs less than the same
volume of the substance in the liquid state.
d Gases readily mix together.
e The total pressure of a mixture of gases is equal to the sum of the
pressures exerted by each of the gases in the mixture.
2 Use the ideas of the kinetic molecular theory of gases to explain the
following observations.
a Tyre manufacturers recommend a maximum pressure for tyres.
b The pressure in a car’s tyres will increase if a long distance is travelled
on a hot day.
c You can smell dinner cooking as you enter your house.
d A balloon will burst if you blow it up too much.
3 In the kinetic molecular theory, pressure is described as the force per
unit area of surface. Explain what happens to the pressure in each of
the following situations.
a The temperature of a filled aerosol can is increased.
b A gas in a syringe is compressed.
4 Convert each of the following pressures to the units specified.
a 140 kPa to Pa b 92 000 Pa to kPa
c 4.24 atm to mmHg and Pa d 120 kPa to mmHg, atm and bar
e 1400 mmHg to atm, Pa and bar f 80 000 Pa to atm, mmHg and bar
5 Convert the following volumes to the unit specified.
a 2 L to mL b 4.5 L to m3
c 2250 mL to L d 120 mL to L
e 5.6 mL to L f 3.7 m3 to L
g 285 mL to m 3
h 4.70 × 10−3 m3 to L and cm3

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 71


3.2 Universal gas equation
Combustion reactions produce gases. Because the gaseous products may be
harmful to people or to the environment, it is very useful for scientists to be able to
quantify the amount of gas produced by different fuels.
The behaviour of gases has been described qualitatively in section 3.1. In this
section, you will learn about the mathematical relationships that link volume,
pressure, temperature and the number of particles of a gas, and in particular how
to use these relationships to calculate the volumes of gases.
These mathematical relationships were developed over a period of several
hundred years by different scientists who performed experiments on gases. Robert
Boyle, pictured in Figure 3.2.1, experimentally determined the relationship between
the pressure and volume of a gas. Figure 3.2.2 shows Jacques Charles, who identified
the relationship between the volume and temperature of a gas. In 1787, Charles
determined that the volume of a fixed amount of gas is directly proportional to
the absolute temperature, provided the pressure remains constant. The relationship
between gas volume and temperature is known as Charles’ law.
FIGURE 3.2.1
These relationships have become known as the gas laws. The gas laws are used
to describe the behaviour of all gases, regardless of their chemical composition.

VOLUME AND PRESSURE


Changing the volume of a fixed amount of gas at constant temperature causes a
change in the pressure of the gas. The pressure of the gas in the syringe shown in
(a) (b) Figure 3.2.3 increases as the plunger is pushed in and decreases as the plunger is
pulled out.

Volume is decreased.
Particles are less
widely spaced.
Pressure increases.

Volume is increased.
FIGURE 3.2.2 Particles are more
widely spaced.
Pressure decreases.

FIGURE 3.2.3

For a given amount of gas at constant temperature, the volume of the gas is
inversely proportional to its pressure. This relationship is seen in the changing
volume of a weather balloon as it rises to altitudes with much lower pressure than
at ground level. A weather balloon filled with helium gas to a volume of 40 L at a
pressure of 1 atm increases in volume to 200 L by the time it reaches an altitude
with a pressure of 0.2 atm.

The mathematical relationship between the pressure, P, exerted by a gas and


the volume, V
P∝1
V
This relationship can also be expressed as PV = k, where k is a constant at a
given temperature.

72 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


VOLUME AND TEMPERATURE
The kinetic molecular theory states that increasing the temperature of a gas
increases the average kinetic energy of the molecules. The molecules move more
rapidly and collide with the walls of the container more frequently and with greater
force. This can cause the:
• volume of gas to increase, if the pressure on the gas remains the same, such as a
gas in a syringe or balloon
• pressure to increase, if the volume of the gas container is fixed, such as in a
sealed flask or a gas cylinder.
Table 3.2.1 shows the results of an experiment that investigates the relationship
between temperature and the volume of a given amount of gas. In this experiment,
the gas in a syringe is heated slowly in an oven. The pressure on the plunger of the
syringe is held constant.

TABLE 3.2.1

Temperature (°C) 20 40 60 80 100 120 140

Volume (mL) 60.0 64.1 68.2 72.3 76.4 80.5 84.6

The graph of these results is linear, as shown in Figure 3.2.4. When the graph
is extrapolated to a volume of 0  L, it crosses the temperature axis at –273°C. If
the origin is reset at –273°C, this graph passes through the origin. This has led
scientists to develop a new temperature scale, known as the kelvin scale or
absolute temperature scale. On the kelvin scale, each temperature increment is
equal to one temperature increment on the Celsius scale, and 0°C is equal to 273 K.

FIGURE 3.2.4 100°C 373 K boiling point of water


at sea level
The relationship between temperature on the Celsius scale and temperature on
the kelvin scale is given by the equation: 0°C 273 K melting point of water
T (in K) = T (in °C) + 273
The temperature 0 K (–273°C) is the lowest temperature theoretically possible. –90°C 183 K coldest temperature
For this reason, 0 K is known as absolute zero. At this temperature, all molecules (approximate) on
and atoms have minimum kinetic energy. Therefore, a temperature in degrees Earth (Antarctica)
Celsius is converted to absolute temperature in kelvin by adding 273. For example,
the boiling point of water at sea level is converted to absolute temperature by adding
273, so 100°C is equivalent to 373 K (Figure 3.2.5). –273°C 0K absolute zero

FIGURE 3.2.5
T (in K) = T

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 73


Extremely low temperatures, within 1 × 10–10 K of absolute zero, have been
reached in the laboratory. Note that the kelvin scale has no degrees sign—it is
written as just K.

CHEMFILE
William Thomson

°
A marine engineering enthusiast, Thomson invented several marine instruments to

FIGURE 3.2.6

The ascending hot-air balloon in Figure 3.2.7 demonstrates the relationship


between volume and temperature. Heating the air causes the balloon to expand,
which reduces the density of the air inside, and allows the balloon to rise.

As the temperature, T, of a gas increases, the volume, V, of the gas increases.


Therefore, V and T
V∝T
V
This relationship can also be expressed as = k, where k is a constant at a given
T
pressure. Note that the value of T must be expressed in kelvin, not degrees
Celsius.

Worked example 3.2.1


CONVERTING TEMPERATURES FROM CELSIUS TO KELVIN

What is 300°C on the kelvin temperature scale?

Thinking Working

T (in K) = T (in °C) + 273 T (in K) = T (in °C) + 273


= 300 + 273
= 573 K

Worked example: Try yourself 3.2.1


FIGURE 3.2.7 CONVERTING TEMPERATURES FROM CELSIUS TO KELVIN

What is 100°C on the kelvin temperature scale?

74 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


VOLUME AND AMOUNT OF GAS The mathematical relationship
The volume, V, occupied by a gas also depends directly on the amount of gas, n, between the volume, V, occupied
in moles. by a gas and the amount of gas,
This relationship is shown in Figure 3.2.8. Both syringes show a gas at a constant n, at constant temperature and
temperature and pressure. The volume doubles with twice the number of molecules
of gas in the syringe. V∝n
This relationship can also be
V
expressed as = k, where k is a
Air pressure n
is constant. constant at a given temperature

Air pressure
is constant.

FIGURE 3.2.8

MOLAR VOLUME OF A GAS


If the amount of gas is fixed at 1 mole as shown in Figure 3.2.9, the volume it
occupies depends almost entirely on its temperature and pressure. We define this
volume as the molar volume, Vm , of a gas. Molar volume is the amount of space,
or volume, occupied by 1 mole of any gas at a particular pressure and temperature.

22.7 L 22.7 L 22.7 L

1 mole of neon, Ne 1 mole of nitrogen, N2 1 mole of ozone, O3


P = 100 kPa P = 100 kPa P = 100 kPa
T = 0°C T = 0°C T = 0°C
V = 22.7 L V = 22.7 L V = 22.7 L
number of molecules = 6.02 × 1023 number of molecules = 6.02 × 1023 number of molecules = 6.02 × 1023
mass = 20.2 g mass = 28.0 g mass = 48.0 g

FIGURE 3.2.9

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 75


The volume of 1 mole of gas, Vm, is equal to its total volume, V, divided by the
number of moles, n, of gas present. This can be represented by the relationship:
V
Vm = (at a given temperature and pressure)
n
Or, by rearranging this expression:

V
n= (at a given temperature and pressure)
Vm

The molar volume of a gas varies with temperature and pressure. However,
molar volume does not vary with the identity of the gas. For example, 1 mole
of hydrogen gas occupies the same volume as 1 mole of oxygen gas at the same
temperature and pressure.

Standard conditions
A temperature of 25°C (298 K) and a pressure of 100 kPa is typical of the conditions
you will encounter when you are working in a laboratory. These conditions are
known as standard laboratory conditions (SLC).
Table 3.2.2 shows the molar volume of an ideal gas and of helium at SLC.
An ideal gas is a theoretical gas composed of particles that do not interact except
during elastic collisions. At SLC, most gases behave very like an ideal gas and,
therefore, have a molar volume very close to that of an ideal gas.

TABLE 3.2.2

Gas Formula Molar volume at SLC (L mol–1)

Ideal gas – 24.79

Helium He 24.83

It is usual to assume that the molar volume of a gas is 24.8 L mol–1 at SLC.
From this value, you can calculate the amount, in moles, of a gas given its volume
at SLC.
Another set of commonly used standard conditions is standard temperature
and pressure (STP). STP refers to a temperature of 0°C (273 K) and a pressure
of 100 kPa. The molar volume of an ideal gas at STP is 22.7 L mol–1.

–1
Vm
–1
Vm

In section 3.4, you will see that when comparing the combustion of different
fuels, the concept of molar volume is often used to determine the volume of oxygen
gas required and the volume of gases produced.

76 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Worked example 3.2.2
CALCULATING THE VOLUME OF A GAS FROM ITS AMOUNT (IN MOL)

Calculate the volume, in L, occupied by 0.24 mol of nitrogen gas at SLC.


Assume that nitrogen behaves like an ideal gas.

Thinking Working
V V
Rearrange n = to make volume the subject. n=
Vm Vm
V = n × Vm

Substitute in the known values where V = n × Vm


Vm = 24.8 L mol–1 (at SLC) and solve. = 0.24 × 24.8
= 5.952 L

Consider the units and significant figures. V = 6.0 L


The answer should be given to the
smallest number of significant figures in
the measurement.

Worked example: Try yourself 3.2.2


CALCULATING THE VOLUME OF A GAS FROM ITS AMOUNT (IN MOL)

Calculate the volume, in L, occupied by 3.5 mol of oxygen gas at SLC. Assume


that oxygen behaves like an ideal gas.

THE UNIVERSAL GAS EQUATION


The following three laws describe the behaviour of gases under different conditions:
1
• V ∝ (for constant T and n)
P
• V ∝ T (for constant P and n)
• V ∝ n (for constant P and T)
We can combine all three laws by writing:
nT
V∝
P
RnT
This relationship can be expressed as V = , where R is a proportionality
P
constant.

The equation is known as the universal gas equation and is more usually

PV = nRT
where R is called the universal gas constant, or simply, the .

This constant can be determined experimentally by measuring the volume


occupied by a known amount of gas at a known temperature and pressure.

The value of R depends on the units of pressure and volume used. It has a value
of 8.31 J K–1 mol–1
• P
• V
• n
• T

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 77


You will use the universal gas equation in section 3.4 to calculate the volume of
oxygen gas consumed and the volume of gases produced during the combustion
of different fuels.

Worked example 3.2.3


CALCULATING THE VOLUME OF A GAS USING THE UNIVERSAL GAS EQUATION

Calculate the volume, in L, occupied by 2.24 mol of oxygen gas (O2) if the


pressure is 200 kPa at 50°C.

Thinking Working

Convert units, if necessary. P = 200 kPa (no conversion required)


Pressure is in kPa and T = 50 + 273
temperature in K.
= 323 K

Rearrange the universal gas PV = nRT


equation so that volume, V, nRT
is the subject. V=
P
Substitute values for pressure, 2.24 × 8.31 × 323
V=
amount, temperature and the 200
gas constant, R, then solve = 30.1 L
for V. Express the answer to the
correct number of significant
figures.

Worked example: Try yourself 3.2.3


CALCULATING THE VOLUME OF A GAS USING THE UNIVERSAL GAS EQUATION

Calculate the volume, in L, occupied by 13.0 mol of carbon dioxide gas (CO2) if


the pressure is 250 kPa at 75.0°C.

CHEMISTRY IN ACTION

Decompression chambers
Scuba diving and water pressure Scuba diving and gas solubility
If you swim at the water’s surface, your body experiences a As the pressure in a diver’s lungs increases during a dive,
pressure, due to the surrounding air, of about 1 atm. Below more gas dissolves in the blood. Nitrogen (N2) is one of
the surface, your body experiences an additional pressure these gases. When a diver ascends, the pressure drops,
due to the water. This additional pressure amounts to the nitrogen becomes less soluble in the blood and so
about 1 atm for every 10 m of depth. Therefore, at 20 m comes out of solution. If a diver ascends too quickly, the
the pressure on your body is about 3 atm. rapid pressure drop causes the nitrogen to come out of the
As the pressure on your body increases, the volume blood as tiny bubbles (see Figure 3.2.10a). This is similar
of your body cavities such as your lungs and inner to the bubbles of carbon dioxide you observe when you
ears decreases. This squeezing effect makes diving open a bottle of soft drink.
well below the water’s surface without scuba equipment These bubbles cause pain in joints and muscles. If they
very uncomfortable. Scuba equipment overcomes this form in the spinal cord, brain or lungs, they can cause
problem by supplying air from tanks to the mouth at the paralysis or death. Treatment for divers suffering from
same pressure as that produced by the underwater this effect (the bends) involves time in a decompression
environment. chamber similar to the one shown in Figure 3.2.10b.

78 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


(a)

A slow return to the surface


0 metres lets the nitrogen return to
pressure = 1 atm the lungs where it is
breathed out.

Swimming up too
quickly doesn’t give the
nitrogen enough time to
10 metres leave the blood—instead
pressure = 2 atm it can form painful
bubbles.

Nitrogen moves from the


lungs (high pressure) into the
blood (low pressure).

(b)

FIGURE 3.2.10

The chamber increases the pressure surrounding the HBOT is also used by athletes for faster recovery from
diver’s body, forcing any nitrogen bubbles to dissolve in soft tissue injuries, to produce sharper performance and
the blood, and then slowly reduces the pressure back to to maintain more intense training schedules. Tennis star
1 atm. The duration of treatment depends on the severity Novak Djokovic uses a hyperbaric chamber to assist with
of the symptoms, the dive history and the patient’s recovery from long, exhausting matches. AFL clubs are
response to treatment. interested in the use of hyperbaric oxygen therapy for
Hyperbaric oxygen therapy (HBOT) is a medical treating soft tissue injuries. One of the earliest cases of
treatment in which patients breathe pure oxygen while hyperbaric oxygen treatment in football was for an ankle
inside a decompression chamber at a pressure higher injury sustained by Carlton midfielder Fraser Brown in
than 1 atm. Its medical uses include improved wound the 1995 preliminary final against North Melbourne.
healing by reduction of swelling, infection control and the Every morning, in the week leading up to the Grand Final,
stimulation of new blood vessel growth. The hyperbaric he spent an hour in a chamber in the hyperbaric unit at
unit at the Alfred Hospital in Melbourne is equipped with the Alfred Hospital. Eventually selected to play in the Grand
three pressurisable hyperbaric rooms used for treating Final, Brown made it through the game with the help of
the bends, ulcers, soft tissue infections, carbon monoxide strapping and pain-killing injections, helping Carlton win
poisoning and wounds that won’t heal such as those the premiership.
resulting from diabetes or radiotherapy.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 79


3.2 Review
SUMMARY

• The following three laws describe the behaviour of • The molar volume, Vm, of a gas is the volume
gases under different conditions: occupied by 1 mol of gas at a given temperature
1 and pressure:
– V ∝ (for constant T and n)
P V
– V ∝ T (for constant P and n) n=
Vm
– V ∝ n (for constant P and T) • The value of Vm is 24.8 L mol–1 at SLC.
• Absolute zero is a temperature of –273°C or 0 K. • The value of Vm is 22.7 L mol–1 at STP.
Molecules and atoms have minimum kinetic energy • PV = nRT is the universal gas equation. It can be
at this temperature. used to calculate one variable (P, V, n or T) when
• Standard laboratory conditions (SLC) refers to a the other three variables are known.
temperature of 25°C (298 K) and a pressure of • R is the universal gas constant and its value is
100 kPa. 8.31 J K–1 mol–1 when pressure is in kPa, volume
• Standard temperature and pressure (STP) refers is in L, amount is in mol and temperature is in K.
to a temperature of 0°C (273 K) and a pressure of
100 kPa.

KEY QUESTIONS

1 Convert the following Celsius temperatures to absolute temperatures.


a 100°C
b 175°C
c −145°C
2 Calculate the volume of the following gases at SLC.
a 1.4 mol of chlorine (Cl2)
b 1.0 × 10−3 mol of hydrogen (H2)
c 1.4 g of nitrogen (N2)
3 Calculate the mass of the following gas samples. All volumes are measured
at SLC.
a 2.80 L of neon (Ne)
b 50.0 L of oxygen (O2)
c 140 mL of carbon dioxide (CO2)
4 0.25 mol of nitrogen is placed in a flask of volume 5.0 L at a temperature
of 5°C. What is the pressure in the flask?
5 What volume of gas, in litres, is occupied by:
a 0.20 mol of hydrogen at 115 kPa and 40°C?
b 12.5 mol of carbon dioxide at 5 atm and 150°C?
c 8.50 g of hydrogen sulfide (H2S) at 100 kPa and 27°C?
6 Calculate the mass of helium in a balloon if the volume is 100 L at a
pressure of 95 000 Pa and a temperature of 0°C.
7 At a given temperature, a sample of nitrogen, of mass 11.3 g, exerts a
pressure of 102 kPa in a gas cylinder of volume 10.0 L. Calculate the
temperature of the gas.
8 Which sample of gas contains the greater amount, in mol, of gas: 3.2 L of
nitrogen at 25°C and a pressure of 1.2 bar or 2.5 L of helium at 23°C and a
pressure of 1.2 atm?

80 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


3.3 Calculations involving
combustion of fuels—Part 1
Measuring and predicting quantities is a very important part of chemistry. Scientists
compare fuels by calculating the quantities of chemicals involved in reactions.
The  ethanol produced in the plant shown in Figure 3.3.1 can be compared to
petroleum by calculating how much oxygen is required for complete combustion.
How much atmospheric pollution a fuel will produce can be determined by
calculating the mass of carbon emissions.
In this section you will learn about these types of calculations.

STOICHIOMETRY AND REACTIONS OF FUELS


Calculations that involve the use of the mole concept, combined with an
understanding of chemical equations, are called stoichiometric calculations. In this
section and section 3.4, you will use these calculations for reactions involving fuels,
but stoichiometry is important in all areas of chemistry.
Stoichiometry is the study of ratios of moles of substances. Stoichiometric
calculations are based on the law of conservation of mass. FIGURE 3.3.1

In a chemical reaction, the total mass of all products is equal to the total mass

Another way of expressing this is that, in a chemical reaction, atoms are neither
created nor destroyed. Consequently, given the amount of one substance involved
in a chemical reaction and a balanced equation for the reaction, you can calculate
the amounts of all other substances involved.

Equations and reacting amounts


Consider the equation for the reaction that occurs when methane (CH4) burns
in oxygen:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
The coefficients used to balance the equations show the ratios between the
reactants and products involved in the reaction. The equation indicates that 1 mole
of CH4(g) reacts with 2 moles of O2(g) to form 1 mole of CO2(g) and 2 moles of
H2O(g). In more general terms, the amount of oxygen used will always be double
the amount of methane used, double the amount of carbon dioxide produced and
the same as the amount of water vapour produced.
n(O2) 2 n(CO2) 1 n(H2O) 2
= , = and = =1
n(CH4) 1 n(O2) 2 n(O2) 2
In general, for stoichiometric calculations you will be told, or you will be able
to work out, the number of moles of one chemical in the reaction (the ‘known’).
You will then need to calculate the number of moles of another chemical (the
‘unknown’).
You can write the relationship between the known and unknown chemicals
using ratios:

n(unknown chemical) coefficient of unknown chemical


=
n(known chemical) coefficient of known chemical

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 81


Worked example 3.3.1
USING MOLE RATIOS

How many moles of carbon dioxide are generated when 24 moles of propane
(C3H8) are burned completely in oxygen?

Thinking Working

Write a balanced equation for C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)


the reaction.

Note the number of moles of the n(C3H8) = 24 mol


known substance.

Write a mole ratio for: n(CO2) 3


=
coefficient of unknown n(C3H8) 1
coefficient of known
Calculate the number of moles of the 3
n(CO2) = × 24
unknown substance using: 1
n(unknown) = mole ratio × n(known) = 72 mol

USING MOLE RATIOS

How many moles of carbon dioxide are generated when 0.50 moles of butane
(C4H10) are burned completely in oxygen?

When carrying out any stoichiometric calculations, you must always clearly state
the mole ratio for the reaction you are working with.

Mass–mass stoichiometry
Calculations can require you to start and finish with masses rather than moles, as
this is how quantities of chemicals are often measured. To calculate the number of
moles from the mass of a substance, use this relationship:

mass in g (m)
moles (n) =
molar mass (M)

and to calculate a mass, rearrange this relationship as:

mass in g (m) = number of moles (n) × molar mass (M)

Stoichiometric calculations generally follow the same pattern. The number


of moles of a ‘known’ substance is calculated from data that is given to you, the
mole ratios in the equation are used to find the number of moles of the ‘unknown’
substance, and the desired quantity of the unknown substance is then calculated.
These steps and details of formulas used when performing stoichiometric
calculations involving the combustion of fuels are summarised in Figure 3.3.2.

82 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


mass of known m mass of unknown
n= m=n×M
substance (g) M substance (g)
V from
n=
volume of known Vm mole of known mole of unknown V = n × Vm volume of unknown
gas at SLC (L) substance (n) in chemical substance (n) gas at SLC (L)
PV nRT
n= equation V=
RT P
volume of
volume of unknown
known gas at
gas at non-standard
non-standard
conditions (L)
conditions (L)

FIGURE 3.3.2

When carrying out stoichiometric calculations, always keep the answer in your
calculator and proceed to the next step. Only round to the correct number of

Worked example 3.3.2


SOLVING MASS–MASS STOICHIOMETRIC PROBLEMS

Calculate the mass of carbon dioxide, in kg, produced when 540 g of propane
(C3H8) are burned completely in oxygen.

Thinking Working

Write a balanced equation for C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)


the reaction.

Calculate the number of moles 540


n(C3H8) =
of the known substance using: 44.0
m
n= = 12.3 mol
M
Find the mole ratio: n(CO2) 3
=
coefficient of unknown n(C3H8) 1
coefficient of known
Calculate the number of moles 3
n(CO2) = × 12.3
of the unknown substance using: 1
n(unknown) = mole ratio × n(known) = 36.8 mol

Calculate the mass of the unknown m(CO2) = 36.8 × 44.0


substance using: = 1620 g
m=n×M = 1.62 kg

Worked example: Try yourself 3.3.2


SOLVING MASS–MASS STOICHIOMETRIC PROBLEMS

Calculate the mass of carbon dioxide produced when 3.60 kg of butane (C4H10)
is burned completely in oxygen.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 83


3.3 Review
SUMMARY

• A balanced equation shows the ratio of the amount, n(unknown chemical)


=
in moles, of reactants and products in the reaction. n(known chemical)
coefficient of unknown chemical
• Mass–mass stoichiometric calculations follow the
coefficient of known chemical
general steps:
3 Find the mass of the unknown substance from
1 Calculate the amount, in moles, of a known
its amount, in moles, using m = n × M.
substance from the mass provided using:
m • Stoichiometric calculations can be used to calculate
n= the mass of carbon dioxide and water released
M
2 Use the mole ratio from a balanced chemical during the combustion of a carbon-based fuel
equation to determine the amount, in moles, and the mass of oxygen required for complete
of the unknown substance. combustion.

KEY QUESTIONS

1 Methanol burns in air according to the equation:


2CH3OH(g) + 3O2(g) → 2CO2(g) + 4H2O(g)
Complete the following mathematical relationships:
n(CH3OH) n(O2) n(CH3OH)
a = b = c =
n(O2) n(H2O) n(CO2)
2 Create a flowchart for completing mass–mass stoichiometric calculations
by placing the steps in the correct order.
• Identify the known and unknown substances in the question.
• Use mole ratios from the equation to calculate the amount of the
unknown substance.
• Calculate the mass of the unknown substance using m = n × M.
• Write a balanced equation for the reaction.
m
• Calculate the amount, in mol, of the known substance using n = .
M
3 Octane (C8H18) is a component of petrol. It burns in oxygen to produce
carbon dioxide and water. Energy is released during this reaction.
The equation for this reaction is:
2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(g)
a Calculate the mass of oxygen required to react with 200 g of octane.
b Calculate the mass of carbon dioxide produced in part a.
4 Propane burns in oxygen according to the equation:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
6.70 g of propane was burned in excess oxygen.
a What mass of carbon dioxide would be produced?
b What mass of oxygen would be consumed in the reaction?
c What mass of water would be produced?
5 A combustion reaction occurred in which 1.00 kg of butane (C4H10) reacted
with excess oxygen gas.
a Calculate the mass of oxygen, in kg, required for the complete
combustion of this amount of butane.
b Calculate the mass of carbon dioxide, in kg, produced in this reaction.

84 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


3.4 Calculations involving
combustion of fuels—Part 2
In section 3.3 you learned how to use stoichiometric calculations to find the mass
of chemicals consumed or produced when fuels are burned. In this section, you will
use stoichiometry to calculate the volumes of oxygen required to burn fuels and the
volumes of gases produced by the reactions. Carbon dioxide emissions from power
plants such as the one shown in Figure 3.4.1 can be calculated using stoichiometry.

FIGURE 3.4.1

MASS–VOLUME STOICHIOMETRY
Some stoichiometric calculations require you to determine the volume of a gas that
reacts with, or is produced from, a given mass of a fuel during combustion. For
these calculations, you need to determine the number of moles of the fuel from its
mass, and use the mole ratio from the balanced chemical equation.
The volume of the gas, in litres, is determined from its amount, in moles, using
one of the following formulas.
1 At standard laboratory conditions of 25°C and 100 kPa (SLC), the molar
volume equation is used:
V
n=
Vm
This formula can be rearranged to make volume the subject:
V = n × Vm
Remember that at SLC, the accepted volume of one mole of any gas is
24.8 L mol–1.
2 At non-standard conditions, the universal gas equation is used:
PV = nRT
The universal gas equation can also be rearranged to make volume the subject:
nRT
V=
P
Remember that for use in the universal gas equation, pressure must be in kPa,
temperature must be in K and the gas constant is equal to 8.31 J K–1 mol–1.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 85


Worked Examples 3.4.1 and 3.4.2 show how to calculate the volume of carbon
dioxide that is produced from a known mass of fuel at SLC and at non-standard
conditions.

Worked example 3.4.1


MASS–VOLUME STOICHIOMETRIC CALCULATIONS AT STANDARD LABORATORY
CONDITIONS

Calculate the volume of carbon dioxide, in L, produced when 2.00 kg of propane


is burned completely in oxygen. The gas volume is measured at SLC.

Thinking Working

Write a balanced equation for C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)


the reaction.

Calculate the number of moles of the 2000


n(C3H8) =
known substance using: 44.0
m = 45.5 mol
n=
M
Find the mole ratio: n(CO2) 3
=
coefficient of unknown n(C3H8) 1
coefficient of known
Calculate the number of moles of the 3
n(CO2) = × 45.5
unknown substance using: 1
n(unknown) = mole ratio × n(known) = 136 mol

Calculate the volume of the unknown V(CO2) = 136 × 24.8


substance using: = 3382 L
V = n × Vm = 3.38 × 103 L

MASS–VOLUME STOICHIOMETRIC CALCULATIONS AT STANDARD LABORATORY


CONDITIONS

Calculate the volume of carbon dioxide, in L, produced when 300 g of butane


is burned completely in oxygen. The gas volume is measured at SLC.

Worked example 3.4.2


MASS–VOLUME STOICHIOMETRIC CALCULATIONS AT NON-STANDARD
CONDITIONS

Calculate the volume of carbon dioxide, in L, produced when 800 g of propane


is burned completely in oxygen. The gas volume is measured at 60°C and
200 kPa.

Thinking Working

Write a balanced equation for C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)


the reaction.

Calculate the number of moles of the 800


n(C3H8) =
known substance using: 44.0
m = 18.2 mol
n=
M
Find the mole ratio: n(CO2) 3
=
coefficient of unknown n(C3H8) 1
coefficient of known

86 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Calculate the number of moles of the 3
n(CO2) = × 18.2
unknown substance using: 1
n(unknown) = mole ratio × n(known) = 54.5 mol

Express the pressure and temperature P = 200 kPa


in required units. T = 60 + 273
= 333 K

Calculate the volume of the unknown 54.5 × 8.31 × 333


V(CO2) =
substance using: 200
nRT = 755 L
V=
P

Worked example: Try yourself 3.4.2


MASS–VOLUME STOICHIOMETRIC CALCULATIONS AT NON-STANDARD
CONDITIONS

Calculate the volume of carbon dioxide, in L, produced when 5.00 kg of butane is


burned completely in oxygen. The gas volume is measured at 40°C and 400 kPa.

GAS VOLUME–VOLUME CALCULATIONS


For chemical reactions where both the reactants and products are in the gaseous
state, it is often convenient to measure volumes, rather than masses. This is the case
for the combustion of a number of fuels.
For example, the reaction between propane gas and oxygen can be represented
by the equation:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
This equation tells us that when 1 mole of propane reacts with 5 moles of oxygen
gas, 3 moles of carbon dioxide and 4 moles of water vapour are produced.
You saw in section 3.2 that equal amounts, in moles, of all gases occupy equal
volumes measured at the same temperature and pressure.
Therefore, the mole ratios in the balanced equation become volume ratios at the
same temperature and pressure. In the above reaction, this means that when 1 litre
of propane gas reacts with 5 litres of oxygen gas, 3 litres of carbon dioxide and
4 litres of water vapour are produced.

Worked example 3.4.3


GAS VOLUME–VOLUME CALCULATIONS

Methane gas (CH4) is burned in a gas stove according to the following equation:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
If 50 mL of methane is burned, calculate the volume of O2 gas required for
complete combustion of the methane under constant temperature and pressure
conditions.

Thinking Working

Use the balanced equation to find 1 mol of CH4 gas reacts with 2 mol of
the mole ratio of the two gases O2 gas.
involved.

The temperature and pressure are 1 volume of CH4 reacts with 2 volumes
constant, so volume ratios are the of O2 gas, so 50 mL of CH4 reacts with
same as mole ratios. 100 mL of O2.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 87


Worked example: Try yourself 3.4.3
GAS VOLUME–VOLUME CALCULATIONS

Methane gas (CH4) is burned in a gas stove according to the following equation:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
If 50 mL of methane is burned in air, calculate the volume of CO2 gas produced
under constant temperature and pressure conditions.

EXTENSION

Calculations involving excess reactants


As you learned in Unit 2 Chemistry, stoichiometry calculations become more
complex if the reactants are not present in their stoichiometric ratio. In these
cases, you must determine which reactant is completely consumed in the
Always use the number of
reaction, the limiting reactant, and which one is present in excess. The amount
moles of the limiting reactant
to determine the amount of of limiting reactant determines how much product is formed.
Worked Example 3.4.4 introduces a strategy that can be used to determine
the limiting reactant in a reaction.

Worked example 3.4.4


EXCESS REACTANT CALCULATIONS
A gaseous mixture of 25.0 g of hydrogen gas and 100.0 g of oxygen gas are
mixed and ignited. The water produced is collected and weighed. What is the
expected mass of water produced? The equation for the reaction is:
2H2(g) + O2(g) → 2H2O(g)

a Which reactant is the limiting reactant?


b What is the mass of water vapour formed?

Thinking Working

a Calculate the number of moles m


n(H2) =
of each reactant using M
m V PV 25.0
n= or n = or n = =
M Vm RT 2.0
as appropriate. = 12.5 mol
m
n(O2) =
M
100.0
=
32.0
= 3.13 mol

88 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Use the coefficients of the equation The equation shows 2 mol of H2
to find the limiting reactant. reacts with 1 mol of O2.
So to react all of the O2 will require
2 × n(O2) of H2
= 2 × 3.13
= 6.26 mol
As there is 12.5 mol of H2, the H2
is in excess.
The O2 is the limiting reactant (it
will be completely consumed).

b Find the mole ratio using: n(H2O) 2


=
coefficient of unknown n(O2) 1
coefficient of known
The limiting reactant is the known
substance.

Calculate the number of moles n(H2O) = 2 × 3.13


of the unknown substance using: = 6.25 mol
n(unknown) = mole ratio × n(known)

Calculate the required quantity m(H2O) = 6.25 × 18.0


of the unknown using = 113 g
V
m = n × M or n = or PV = nRT
Vm
as appropriate.

Worked example: Try yourself 3.4.4


EXCESS REACTANT CALCULATIONS
Calculate the volume of carbon dioxide, in L, produced when 65.0 g of butane
is burned completely in 200 L of oxygen. The gas volume is measured at SLC.
The equation for the reaction is:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l)

a Which reactant is the limiting reactant?


b What is the volume of carbon dioxide formed?

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 89


3.4 Review
SUMMARY

• A balanced equation shows the ratio of the amount, 3 Find the desired quantity of the unknown
in moles, of reactants and products in the reaction. substance from its amount, in moles, using
• Stoichiometric calculations follow the general steps: m = n × M, V = n × Vm or PV = nRT
1 Calculate the amount, in moles, of a known • The mole ratio in a balanced equation is also a
substance from the data given. volume ratio if all reactants and products are in the
m V PV gaseous state and the temperature and pressure are
Use n = , n = or n =
M Vm RT kept constant.
2 Use the mole ratio from a balanced chemical • Stoichiometric calculations can be used to calculate
equation to determine the amount, in moles, of the volume of carbon dioxide and water released
the unknown substance. during the combustion of a carbon-based fuel
n(unknown chemical) and the volume of oxygen required for complete
=
n(known chemical) coefficient of unknown chemical combustion.
coefficient of known chemical

KEY QUESTIONS

1 Propane (C3H8) burns in oxygen according to the equation:


C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
When the following masses of propane react completely with excess oxygen,
calculate the volume of:
i oxygen used at SLC
ii carbon dioxide produced at SLC.
a 22 g
b 16.5 g
c 3.40 kg
2 Octane is one of the main constituents of petrol. It burns according to
the equation:
2C8H18 (g) + 25O2(g) → 16CO2(g) + 18H2O(g)
What mass of octane must have been used if 50.0 L of carbon dioxide,
measured at 120°C and 1.10 atm, was produced?
3 Hydrogen peroxide decomposes according to the equation:
2H2O2(aq) → 2H2O(l) + O2(g)
Calculate the volume of oxygen, collected at 30.0°C and 91.0 kPa, that is
produced when 10.0 g of hydrogen peroxide decomposes.
4 What volume of NO2 is produced when 0.5 L of nitrogen(II) oxide (NO) reacts
with excess oxygen? (All volumes are measured at 25°C and 100 kPa.)
The equation for the reaction is:
2NO(g) + O2(g) → 2NO2(g)
5 Calculate the volume of oxygen needed to completely react with 150 mL of
carbon monoxide according to the following equation. Assume all volumes
are measured at the same temperature and pressure.
2CO(g) + O2(g) → 2CO2(g)

90 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


3.5 Calculations involving energy
changes
The combustion of fuels provides us with energy for daily use, including heat for
warmth and cooking, and a source of power for transport.
The amount of energy released when a fuel burns is directly proportional to the
amount of fuel consumed. The bonfire shown in Figure 3.5.1 contains more fuel
than the match, so it releases more energy. Doubling the quantity of petrol in a car
allows you to travel twice as far.

FIGURE 3.5.1

In Chapter 2 you learned that thermochemical equations show the energy


released or absorbed during a chemical reaction by including a sign and numerical
value for the heat change that occurs in the reaction represented by the equation.
You can use thermochemical equations to calculate the energy released by the
combustion of specified quantities of fuel. You will learn how to do these types of
calculations in this section.

COMBUSTION AND ENERGY


The amount of energy released by the combustion of fuels depends on:
• the type of fuel burned
• the amount of fuel burned
• whether complete combustion or incomplete combustion is involved.
Consider the thermochemical equations for the complete combustion of
methane and pentane:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = –890 kJ mol–1
C5H12(g) + 8O2(g) → 5CO2(g) + 6H2O(l) ∆H = –3509 kJ mol–1
The equations show us that the combustion of one mole of pentane (C5H12)
releases much more energy than the combustion of one mole of methane (CH4).
Complete combustion occurs when there is a plentiful oxygen supply. Incomplete
combustion occurs when the oxygen supply is limited, and carbon monoxide is
formed rather than carbon dioxide. The complete combustion of a fuel releases
more energy than incomplete combustion of the same amount. For example,
for ethane:
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) ∆H = –3120 kJ mol–1
2C2H6(g) + 5O2(g) → 4CO(g) + 6H2O(l) ∆H = –1989 kJ mol–1
CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 91
Calculating energy change from thermochemical equations

enthalpy
change.

For example, the thermochemical equation for the complete combustion of


ethane indicates that 3120 kJ of energy is released by the reaction of 2 moles of
ethane with 7 moles of oxygen.
Worked Examples 3.5.1 and 3.5.2 show you how to use a thermochemical
equation to calculate the energy released by the combustion of different amounts
of fuels or the amount of fuel required to produce a specified amount of energy.

Worked example 3.5.1


CALCULATING ENERGY RELEASED BY THE COMBUSTION OF A PARTICULAR
AMOUNT OF A FUEL

Calculate the heat energy released, in MJ, when 10.0 kg of octane undergoes
complete combustion.
2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(l) ∆H = –10 900 kJ mol–1

Thinking Working

Calculate the amount, in moles, of 10 000


n(C8H18) =
the fuel using: 114.0
m = 87.7 mol
n=
M
Using the thermochemical equation, 2 moles of C8H18 release 10 900 kJ.
write a relationship between the Let 87.7 moles of C8H18 release x kJ.
number of moles of fuel burned
and energy released.

Calculate the energy released by the 87.7 x


By proportion: =
fuel in kilojoules. 2 10 900
87.7
x= × 10 900
2
= 477 965 kJ

Convert the energy released to MJ. 477 965 kJ = 478 MJ


3
1 MJ = 10  kJ

Worked example: Try yourself 3.5.1


CALCULATING ENERGY RELEASED BY THE COMBUSTION OF A PARTICULAR
AMOUNT OF A FUEL

Calculate the heat energy released, in MJ, when 10.0 kg of ethane undergoes
complete combustion.
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) ∆H = –3120 kJ mol–1

92 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Worked example 3.5.2
CALCULATING THE AMOUNT OF FUEL THAT MUST BE BURNED TO PRODUCE
A PARTICULAR AMOUNT OF ENERGY

What volume of methane, measured at SLC, burns completely to provide


4.00 × 104 kJ?
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = –890 kJ mol–1

Thinking Working

Using the thermochemical equation, 1 mole of CH4 releases 890 kJ.


write a relationship between the number Let x moles release 4.00 × 104 kJ.
of moles of fuel burned and energy
released.

Calculate the amount of the fuel that 1 890


By proportion: =
was burned to produce the energy. x 4.00 × 104
4.00 × 104
x=
890
= 44.9 mol

Calculate the volume of the fuel, at SLC. V


n=
Vm
V(CH4) = n × Vm
= 44.9 × 24.8
= 1115 L
= 1.12 × 103 L

Worked example: Try yourself 3.5.2


CALCULATING THE AMOUNT OF FUEL THAT MUST BE BURNED TO PRODUCE
A PARTICULAR AMOUNT OF ENERGY

What volume of methane, measured at SLC, burns completely to provide


5.00 × 103 kJ.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = –890 kJ mol–1

COMPARING FUELS USING STOICHIOMETRIC


CALCULATIONS
Octane (C8H18) and ethanol (C2H5OH) are used as fuels for transport. Octane is
derived from a fossil fuel whereas ethanol is a biofuel. You can use your knowledge
of stoichiometry and thermochemical equations to compare the benefits of the use
of the two fuels by calculating quantities such as the:
• energy released by the same mass of each fuel
• volumes of carbon dioxide and water vapour released by the same mass of
each fuel
• volume of carbon dioxide released per MJ of energy produced for each fuel
• total (net) volume of greenhouse gases released per MJ of energy produced for
each fuel.
Both carbon dioxide and water vapour are greenhouse gases, which absorb
and emit infrared or heat radiation, thus trapping heat in the lower atmosphere.
The thermochemical equations for the complete combustion of the fuels to
form carbon dioxide and water vapour are given below:
Octane: 2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(g) ∆H = –10 108 kJ mol–1
Ethanol: C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g) ∆H = –1235 kJ mol–1

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 93


Calculations for octane are shown below. A comparison of each of these
quantities for octane and ethanol is given in Table 3.5.1 on page 95.

Energy released per kilogram


For 1.00 kg of octane:
m
n(C8H18) =
M
1000
=
114.0
= 8.77 mol
From the equation:
2 moles of C8H18 release 10 108 kJ
Let 8.77 moles of C8H18 release x kJ.
8.77 x
=
2 10 108
8.77
x= × 10 108
2
= 44 333 kJ
= 44.3 MJ
The energy content of octane is 44.3 MJ kg–1.

Volume of CO2
For 1.00 kg of octane:
From the equation:
n(CO2) 16
=
n(C8H18) 2
16
So n(CO2 ) = × 8.77
2
= 70.2 mol
V
n=
Vm
So V = n × Vm
At SLC, V(CO2) = 70.2 × 24.8
= 1.74 × 103 L
Complete combustion of octane produces 1.74 × 103 L kg–1.

Volume of CO2 (a greenhouse gas) released at SLC per MJ of


energy obtained
From the equation:
16 mol of CO2 is released when 10 108 kJ of energy is released.
Calculate the volume occupied by 16 mol of CO2 at SLC:
V
n=
Vm
So V = n × Vm
At SLC, V(CO2) = 16 × 24.8
= 397 L
So, production of 397 L of CO2 releases 10 108 kJ (10.108 MJ).
Let the production of x L of CO2 release 1 MJ of energy.
By proportion:
x 1
=
397 10.108
397
x=
10.108
= 39.3 L
Complete combustion of octane to produce 1  MJ of energy produces 39.3  L of
CO2, measured at SLC.

94 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


Total volume of greenhouse gases (CO2 and H2O) per MJ of

Under these conditions, water will be in the gaseous state.


From the equation:
16 mol of CO2 and 18 mol of H2O (a total of 34 mol of gases) are released when
10 108 kJ of energy is released.
Calculate the volume occupied by 34 moles of gases at 500 K and 1 atm (101.3 kPa):
PV = nRT
nRT
So, V =
P
34 × 8.31 × 500
V(greenhouse gases) =
101.3
= 1395 L
So, production of 1395 L of gases releases 10 108 kJ (10.108 MJ).
Let the production of x L of gases release 1 MJ of energy.
By proportion:
x 1
=
1395 10.108
1395
x=
10.108
= 138 L
Complete combustion of octane to produce 1  MJ of energy produces 138  L of
greenhouse gases, measured at 500 K and 1 atm.

TABLE 3.5.1

Fuel Complete Complete


combustion combustion
of octane of ethanol

Energy content (MJ kg–1) 44.3 26.8

Volume of CO2 per kg produced at SLC (L kg–1) 1.74 × 103 1.08 × 103

Volume of CO2 produced per MJ of energy (L MJ–1) 39.2 40.2

Total volume of greenhouse gases (CO2 and H2O) produced 138 166
per MJ of energy at 500 K and 1 atm (L MJ–1)

The calculations show that octane has a greater energy content than ethanol. On
the other hand, ethanol releases less carbon dioxide per kilogram. Their carbon
dioxide emissions per megajoule of energy produced are similar. However, octane
produces less greenhouse gases overall.
Comparisons such as these assist scientists and engineers to decide on the best
fuel for a particular purpose.

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 95


CHEMFILE
Choosing a fuel

• energy released per unit mass or unit volume

internal combustion engine in cars because it is very costly and

transported and handled more easily and produce less pollution FIGURE 3.5.2

reduce greenhouse gas emissions.

3.5 Review
SUMMARY

• Stoichiometric calculations based on • Thermochemical equations can be used to calculate


thermochemical equations can be used to calculate the volume or mass of greenhouse gases released
the amount of heat energy released during the per MJ of energy obtained.
combustion of a carbon-based fuel. • Fuels can be compared quantitatively in terms of
the amount of energy released and the amount of
carbon emissions released to the environment.

KEY QUESTIONS

1 Which one of the following equations represents the incomplete combustion


of methane?
A 2CH4(g) + 3O2(g) → 2CO(g) + 4H2O(l)
B CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
C C2H6(g) + 2O2(g) → CO(g) + C(s)+ 3H2O(l)
D 2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l)

96 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


2 When petrol is burned in a car engine, the major products of the
combustion reaction are carbon dioxide and water.
a Taking octane (C8H18) as one of the constituents of petrol, write a
balanced equation to represent its combustion to carbon dioxide
and water. Under the conditions in a car engine, octane is a gas and the
water produced is also a gas.
b Sometimes petrol does not burn completely, for example in an engine
that has not been properly tuned. This is because the oxygen supply
is limited and is not sufficient to completely convert the octane to
carbon dioxide and water. Under these conditions, one of the products
of combustion will be carbon monoxide. Write a balanced equation to
show the production of carbon monoxide when octane burns in a limited
supply of oxygen. Assume that carbon monoxide is the only carbon-
containing compound produced.
3 Calculate the energy released when the following quantities of ethane gas
burn according to the equation:
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) ∆H = –3120 kJ mol–1
a 3.00 mol
b 100 g
c 10.0 L at SLC
4 What volume of ethane, measured at SLC, must be burnt according to the
equation in Question 3 in order to yield 100 kJ of heat energy?
5 Calculate the energy released when 250.0 g of petrol burns completely in a
car engine. Assume petrol is mainly octane (C8H18) and burns according to
the equation:
2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(l) ∆H = –10 900 kJ mol–1
6 Butane is used as the fuel in some portable camping stoves. It is a liquid
when stored under pressure in a butane cylinder, but vaporises when the
valve is opened. Combustion of butane is represented by the equation:
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(l) ∆H = –5772 kJ mol–1
a How much energy is produced when 10.0 g of butane burns completely?
b How much energy is produced when 0.100 L of butane, measured at SLC,
burns completely?
c Calculate the volume of butane, measured at 15°C and 108 kPa, that
must be burnt to produce 1.00 kJ of energy.
7 Methane and methanol both burn in air according to the thermochemical
equations:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆H = –890 kJ mol–1
2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O(l) ∆H = –1450 kJ mol–1
a If 1 mole of methane and 1 mole of methanol are completely burned in
separate experiments, which experiment will release the most energy?
b If each of the above reactions is used to produce 2000 kJ of energy,
which fuel will release the most carbon dioxide?

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 97


Chapter review
KEY TERMS

absolute temperature scale ideal gas pressure


absolute zero incomplete combustion standard atmosphere
bar kelvin scale standard laboratory
complete combustion kinetic energy conditions (SLC) universal gas equation
elastic collision kinetic molecular theory standard temperature and velocity
enthalpy molar volume pressure (STP) volume
gas constant partial pressure stoichiometry
greenhouse gas pascal thermochemical equation

Introducing gases 5 a If a container of gas is opened and some of the


1 Which one of the following volumes is equal to 4.5 L? gas escapes, what happens to the pressure of the
A 4.5 × 102 mL remaining gas in the container?
B 4.5 × 103 mL b Use the kinetic molecular theory to explain what
C 4.5 × 10–3 mL happens to the gas pressure in part a.
D 4.5 × 10 mL Universal gas equation
2 Which one of the following best describes the effect of 6 Calculate the mass of oxygen (O2) present in a 50.0 L
an increase in temperature on gas particles? container of oxygen at SLC.
A Both the average kinetic energy and the average 7 Use the molar volume of a gas at SLC to find the:
speed of the particles increase. a volume occupied by 8.0 g of oxygen at SLC
B Both the average kinetic energy and the average b mass of nitrogen dioxide present in 10 L at SLC.
speed of the particles decrease.
8 If 64.0 g of oxygen gas occupies a volume of 25.0 L
C The average kinetic energy of the particles when the temperature is 30.0°C, then the pressure
increases and the average speed of the particles of the gas, in kPa, is closest to:
decreases.
A 20.0
D The average kinetic energy of the particles
B 200
decreases and the average speed of the particles
C 400
increases.
D 6.40 × 103
3 Select the correct answers from the pairs of words to
9 Calculate the volume, in litres, occupied by 10.0 g
complete the paragraph about gases.
of carbon dioxide at 25°C and 101.3 kPa.
The volume occupied by the atoms or molecules
in a gas is much smaller/larger than the total 10 What is the mass of oxygen present in a 10.0 L
volume occupied by the gas. The particles move container of oxygen at a pressure of 105 kPa and
in rapid, straight-line/curved paths and collide at 20°C?
with each other and with the walls of the container. 11 At what temperature will 0.2 g of helium exert a
The forces between particles are extremely weak/ pressure of 80 kPa in a container with a fixed volume
strong. The collisions between particles are elastic/ of 4.0 L?
rigid. The average kinetic energy of the particles is 12 Carbon dioxide gas is a product of the complete
directly/inversely proportional to the temperature combustion of fuels.
of the gas, in units of K/°C. a Calculate the mass of 1.00 mol of carbon dioxide.
4 Use the kinetic theory of gases to explain why: b What is the volume occupied by 1.00 mol of carbon
a the pressure of a gas increases if its volume is dioxide at SLC?
reduced at constant temperature c Given that density is defined as mass/volume,
b the pressure of a gas decreases if its temperature calculate the density of carbon dioxide at SLC
is lowered at a constant volume in g L–1.
c in a mixture of gases, the total pressure is the sum d Would you expect the density of carbon dioxide
of the partial pressure of each gas at STP to be less than, equal to or greater than its
d the pressure of a gas, held at constant volume and density at SLC? Justify your answer.
temperature, will increase if more gas is added to
the container.

98 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?


13 A sample of gas of mass 10.0 g occupies a volume of 20 Octane is one of the main constituents of petrol.
5.4 L at 27°C and 100 × 103 Pa. It burns according to the equation:
a Calculate the amount, in mol, of gas in the sample. 2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(g)
b Determine the molar mass of the gas. Calculate the mass of octane used if 50.0 L of carbon
14 Which container holds more molecules of oxygen gas: dioxide, measured at 120°C and 1.10 atm, was
container A of volume 40.0 L at 25°C and 770 mmHg produced.
or container B of volume 0.10 L at 45°C and 21 What volume of oxygen gas (in L) is required for
390 mmHg? the complete combustion of 10.0 L of ethane gas
15 A room has a volume of 220 m3. at constant pressure and a temperature of 150°C?
a Calculate the amount, in moles, of air particles in 22 Methane burns in excess oxygen according to
the room at 23°C and a pressure of 100 kPa. the equation:
b Assume that 20% of the molecules in the air are CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
oxygen molecules and the remaining molecules This reaction produces 5 L of carbon dioxide at 200°C
are nitrogen. Calculate the mass of air in the room. and 100 kPa. Assuming all volumes are measured at
the same temperature and pressure, calculate the:
Calculations involving combustion of fuels
a volume of methane used
16 Propane (C3H8) burns in oxygen according to the
b volume of oxygen used
equation:
c mass of water vapour produced.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
23 Propane undergoes complete combustion as follows:
6.70 g of propane was burned in excess oxygen.
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
a What mass of carbon dioxide would be produced?
All volumes are measured at 120°C and 102 kPa.
b What mass of oxygen would be consumed in the
When 80 mL of propane and 500 mL of oxygen
reaction?
are reacted:
c What mass of water would be produced?
a one of the gases does not react completely.
17 The ethanol produced by the fermentation of glucose
Which gas is it and what volume of it is unreacted?
is used as a biochemical fuel or biofuel. Fermentation
b what volumes of carbon dioxide and water are
of glucose produces ethanol and carbon dioxide
produced in the reaction?
according to the following equation:
yeast c what change in the total volume of all the gases
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g)
has occurred as a result of the reaction?
Calculate the mass of ethanol produced by the
24 There are many scientists investigating possible fuels
fermentation of 80.0 g of glucose.
to replace fossil fuels. A group of Japanese chemists
18 Large quantities of coal are burned in Australia is investigating the following reaction as a source
to generate electricity, in the process generating of methane:
significant amounts of the greenhouse gas carbon CaCO3(s) + 4H2(g) → CH4(g) + Ca(OH)2(s) + H2O(g)
dioxide. The equation for this combustion reaction is:
At 400°C, 100 kPa and under suitable reaction
C(s) + O2(g) → CO2(g) conditions what:
Determine the mass of carbon dioxide produced by a volume of methane is produced if 100 L of
the combustion of 1.0 tonne (106 g) of coal, assuming hydrogen is completely reacted?
that the coal is pure carbon.
b mass of calcium carbonate is used in part a?
19 Propane (C3H8) burns in oxygen according to the
25 An indoor gas heater burns propane (C3H8) at a rate
equation:
of 12.7 g per minute. Calculate the minimum mass of
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g) oxygen per minute, in g, that needs to be available for
Calculate the volume of: the complete combustion of propane.
i oxygen at SLC used
26 The Hazelwood power station in the Latrobe Valley
ii carbon dioxide at SLC produced consumes about 13.0 million tonnes (1 tonne = 106 g)
when the following masses of propane react of coal in 1 year. The coal used in the power station
completely with excess oxygen. is composed of approximately 25% carbon. Calculate
a 22 g the volume of the greenhouse gas carbon dioxide
b 5.0 g released each year by the power station at SLC.
c 0.145 g
d 16.5 g
e 3.4 kg

CHAPTER 3 | STOICHIOMETRY AND THE COMBUSTION OF FUELS 99


Calculations involving energy changes Connecting the main ideas
27 Calculate the amount of energy released when 806 g 32 Consider two containers of equal size. One contains
of butan-1-ol reacts with excess air according to oxygen and the other carbon dioxide. Both containers
the equation: are at 23°C and at a pressure of 1.0 atm. Answer each
C4H9OH(g) + 6O2(g) → 4CO2(g) + 5H2O(l) of the following questions about the two gases and
∆H = –2677 kJ mol–1 give a reason for your answers.
28 Octane, the principal component of petrol, undergoes a Which of the two samples of gas contains more
combustion with a plentiful supply of oxygen molecules?
according to the equation: b Which of the two samples of gas contains the
2C8H18(l) + 25O2(g) → 16CO2(g) + 18H2O(l) greater number of atoms?
∆H = –10 900 kJ mol–1 c Which of the two gases has the greater density?
a What mass of octane must be burnt in order to 33 Propane burns completely in oxygen according to
yield 100 kJ of energy? the equation:
b Given the density of octane is 0.698 g mL–1, C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)
calculate the energy released when 50.0 L of octane The amount of energy released per tonne of
undergoes complete combustion. carbon dioxide produced is determined to be
29 The complete combustion of propane is represented 1.68 × 104 MJ t –1. Determine the ∆H value, in kJ mol–1,
by the thermochemical equation: for the thermochemical equation. (1 tonne = 106 g)
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) 34 Ethanol can be used as an alternative fuel for
∆H = –2220 kJ mol–1 cars. When ethanol (C2H5OH) undergoes complete
Calculate the energy released per tonne of carbon combustion, it forms carbon dioxide (CO2) and
dioxide produced when propane undergoes complete water (H2O).
combustion. (1 tonne = 106 g) a Write a balanced equation that represents the
30 The equation for the complete combustion of complete combustion of ethanol.
ethane is: b i What mass of carbon dioxide would be formed
2C2H6(g) + 7O2(g) → 4CO2(g) + 6H2O(l) if 1.00 kg of ethanol reacts?
∆H = –3120 kJ mol–1 ii What volume of carbon dioxide would be formed
Calculate the volume of carbon dioxide released at from 1.00 kg of ethanol at SLC?
SLC per MJ of energy generated. c i If the density of ethanol is 0.785 g mL–1,
31 Methane and propane are used as alternative calculate the mass of ethanol in a 50.0 L tank
transport fuels. The heats of combustion of methane of the fuel.
and propane are 890 kJ mol–1 and –2220 kJ mol–1, ii The heat of combustion of ethanol is
respectively. –1367 kJ mol–1. Calculate the energy that can
a Calculate the mass, in kg, of each gas required to be obtained from the complete combustion of
release 100 MJ of energy. 50.0 L of ethanol.
b Calculate the mass of carbon dioxide produced d Calculate the mass of carbon dioxide formed when
by each fuel during the production of 100 MJ 1.00 kJ of energy is released.
of energy.
c Calculate the energy produced per tonne of carbon
dioxide released for each fuel.
d Compare methane and propane as transport fuels
based on the values you calculated in parts a–c.

100 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHAPTER

Redox reactions

Some of the most colourful and exothermic reactions are classified as redox
reactions. This group of reactions includes some that are vitally important
for the functioning of the human body and that provide the energy for our
modern lifestyle.
In this chapter, you will learn how redox reactions can be defined in terms of
electron transfer, and how this definition can be extended by using the concept
of oxidation number. You will find out how to write balanced half-equations that
describe the transfer of electrons, and then how to combine these half-equations
to create an overall equation for the reaction.

Key knowledge
• Redox reactions with reference to electron transfer, reduction and oxidation
reactions, reducing and oxidising agents, and use of oxidation numbers to
identify conjugate reducing and oxidising agents
• The writing of balanced half-equations for oxidation and reduction reactions
and balanced ionic equations, including states, for overall redox reactions

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


4.1 Oxidation and reduction
The highly exothermic reaction between glycerol and potassium permanganate
shown in Figure 4.1.1 is just one example of a redox reaction. Many reactions that
occur in our daily lives are redox reactions. The bleaching of hair, corrosion of
metals, extraction of metals from their ores, combustion of fuels, and reactions in
batteries that produce electrical energy, as well as respiration and photosynthesis,
are all redox reactions.

FIGURE 4.1.1 When glycerol is added to potassium permanganate, a vigorous reaction occurs in
which the glycerol is oxidised by the potassium permanganate.

In this section, you will revise and extend the definitions of oxidation and
reduction that were covered in Unit 2 Chemistry, and learn how they may be applied.

REDOX REACTIONS
Transfer of electrons
In your study of Unit 2 Chemistry you learned that redox reactions (reduction and
oxidation) involve the transfer of electrons from one chemical species to another.
Redox reactions can be considered as occurring in two parts.
In these reactions:
• one of the reactants loses electrons in a process called oxidation
• one of the reactants gains electrons in a process called reduction.
Oxidation and reduction occur simultaneously as electrons are transferred
between the reactants.
Oxidation Is Loss, Reduction Is Gain The mnemonic OIL RIG is a way to remember the difference between oxidation
and reduction processes in terms of electron movement (see Figure 4.1.2).

Reduction and oxidation reactions


You will recall from Unit 1 Chemistry that metals generally have low electronegativities
and their atoms contain 1, 2 or 3 electrons in their valence shells. When a metal
atom loses the electrons in its valence shell, the atom becomes a stable positive ion
FIGURE 4.1.2 The mnemonic OIL RIG is a with the electronic configuration of the nearest noble gas. In comparison, non-
useful way to remember that Oxidation Is the metals have relatively high electronegativities and their atoms generally need to gain
Loss of electrons and Reduction Is the Gain 1, 2 or 3 electrons to achieve the stability of a noble gas electronic configuration.
When non-metal atoms gain electrons, the atoms become negative ions.
102 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Consider the reaction shown in Figure 4.1.3 between aluminium and  iodine.
Aluminium is in group 13 and each atom has 3 electrons in its valence shell, while
iodine is in group 17, so each atom has 7 electrons in its valence shell. When these
two elements react together, each aluminium atom loses 3 electrons and becomes
an Al3+ ion. The aluminium is oxidised. At the same time, each iodine atom gains
1 electron and becomes an I– ion. The iodine is reduced. These two ions form the
ionic compound aluminium iodide.

FIGURE 4.1.3 In a vigorously exothermic reaction, aluminium is oxidised by iodine upon the addition
of a few drops of water, to form aluminium iodide. The heat that is released during the reaction

This reaction can be represented by the equation:


2Al(s) + 3I2(s) → 2AlI3(s)
The oxidation and reduction processes can be clearly seen when you break the
equation into two half-equations. One half-equation describes the oxidation (loss
of electrons) of the aluminium atoms:
Al(s) → Al3+(s) + 3e–
The other half-equation describes the reduction (gain of electrons) of the iodine
atoms:
I2(s) + 2e– → 2I–(s)
The electrons that are gained by the iodine atoms have been lost by the
aluminium atoms.
When you write the overall redox equation, the number of electrons produced
during the oxidation process must be the same as the number of electrons consumed
in the reduction process. You will learn how to write overall redox equations later
in this section.

WRITING REDOX EQUATIONS


Writing simple half-equations
Half-equations show what is happening as electrons are transferred in a redox
reaction. Like other chemical equations, half-equations must be balanced so there
is the same number of atoms of each element on each side of the arrow. Similarly,
charge must also be balanced. Half- and overall equations should also indicate states.
The half-equation for the oxidation of Fe2+(aq) to Fe3+(aq) is written as:
Fe2+(aq) → Fe3+(aq) + e–
Charge is balanced by the addition of an electron to the right-hand side of
the equation.
CHAPTER 4 | REDOX REACTIONS 103
The half-equation for the reduction of Cl2(g) to Cl–(aq) is written as:
Cl2(g) + 2e– → 2Cl–(aq)
Charge is balanced by the addition of two electrons to the left-hand side of
the equation.

Writing an overall redox equation


When writing equations for redox reactions, the two half-equations are normally
written first and then added together to obtain an overall, or full, equation.
The overall equation does not show any electrons transferred; that is, no
electrons appear in a properly balanced full equation. All the electrons lost in the
oxidation reaction are gained in the reduction reaction. You may need to multiply
one, or perhaps both, of the half-equations by a factor to ensure that the electrons
balance and can be cancelled out in the overall equation.

Consider the reaction of iron and chlorine shown in Figure 4.1.4.


In this reaction, each Fe atom is oxidised and loses three electrons. Each Cl2
molecule is reduced and gains two electrons.
Fe(s) → Fe3+(s) + 3e–
Cl2(g) + 2e– → 2Cl–(s)
To write an overall equation for this reaction, the number of electrons lost during
oxidation must equal the number of electrons gained during reduction. Three
electrons are produced by the oxidation of an iron atom but only two electrons are
required to reduce a chlorine molecule. The lowest common multiple of 3 and 2 is
6, so this is the number of electrons that are transferred from iron to chlorine.
The half-equation involving the oxidation of Fe is multiplied by a factor of 2
to bring the total number of electrons to 6 and the half-equation involving the
reduction of Cl2 is multiplied by a factor of 3 to also bring the total number of
electrons to 6.
2Fe(s) → 2Fe3+(s) + 6e–
3Cl2(g) + 6e– → 6Cl–(s)

FIGURE 4.1.4 The reaction between chlorine


and iron is a redox reaction. It is so exothermic
The two half-equations are then added to find the overall equation:
2Fe(s) + 3Cl2(g) → 2FeCl3(s)
You can see that the electrons have been cancelled from each side of the equation
to give the overall equation with no electrons.

Oxidising agents and reducing agents


Substances that cause oxidation to occur are called oxidising agents or oxidants.
In the reaction between aluminium and iodine:
2Al(s) + 3I2(s) → 2AlI3(s)
the iodine is the oxidising agent. An oxidising agent causes oxidation but is always
reduced itself.

104 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Substances that cause reduction are called reducing agents or reductants.
Aluminium is the reducing agent in our example. A reducing agent causes reduction
but is always oxidised itself.
Figure 4.1.5 shows you how to identify the oxidising and reducing agents for the
overall reaction between aluminium and iodine.

Reaction with I2 causes


Al to lose electrons.
I2 is the oxidising agent. Al(s) → Al3+(s) + 3e−
Aluminium is oxidised by iodine.

2Al(s) + 3I2(s) → 2AlI3(s)

Reaction with Al causes I2(s) + 2e− → 2I−(s)


I2 to gain electrons. Iodine is reduced by aluminium.
Al is the reducing agent.

FIGURE 4.1.5 In the reaction between aluminium and iodine, aluminium is the reducing agent and
iodine is the oxidising agent.

Metals, such as zinc and magnesium, and negatively charged non-metal ions,
such as Br– and I–, can lose electrons, so they tend to act as reducing agents:
Zn(s) → Zn2+(aq) + 2e–
2Br–(aq) → Br2(aq) + 2e–

Non-metals, such as fluorine and chlorine, and positively charged metal ions,
such as Cu2+ and Ag+ can gain electrons, so they tend to act as oxidising agents,
for example:
Cl2(g) + 2e– → 2Cl–(aq)
Ag+(aq) + e– → Ag(s)

4.1 Review
SUMMARY

• Redox (reduction–oxidation) reactions involve the • The reducing agent donates electrons to another
transfer of electrons from one species to another. substance, causing that substance to be reduced.
• Oxidation and reduction always occur at the • The oxidising agent accepts electrons from another
same time. substance, causing that substance to be oxidised.
• Half-equations are used to represent oxidation • Half-equations are added together to obtain the
and reduction. overall equation. Before adding the half-equations,
• Oxidation is defined as the loss of electrons, it may be necessary to multiply them by a factor to
e.g. Mg(s) → Mg2+(aq) + 2e–. balance the electrons.
• Reduction is defined as the gain of electrons, • State symbols should always be included in half-
e.g. Cl2(g) + 2e– → 2Cl–(aq). equations and balanced equations for overall redox
reactions.

CHAPTER 4 | REDOX REACTIONS 105


KEY QUESTIONS

1 Complete the summary about redox reactions by using the following terms:
gains, loses, I2, I–, reduced, oxidised.
When a reducing agent, such as Fe, reacts with an oxidising agent, such as
_________, an ionic compound is formed. The reducing agent __________
electrons (is ________ ) and at the same time the oxidising agent __________
electrons (is ________). In this case, the products are Fe2+ and ___________,
which form FeI2.
2 Classify each of the following half-equations as oxidation or reduction.
a 2Br–(aq) → Br2(aq) + 2e–
b Fe2+(aq) → Fe3+(aq) + e–
c Cl2(g) + 2e– → 2Cl–(aq)
d Li(s) → Li+(aq) + e–
e Sn4+(aq) + 2e– → Sn2+(aq)
f Zn2+(aq) + 2e– → Zn(s)
3 When nickel metal reacts with copper(II) ions in an aqueous solution,
nickel(II) ions are formed. Write the oxidation half-equation for the reaction.
4 The overall equation for the reaction between aluminium metal and liquid
sulfur is:
2Al(s) + 3S(l) → Al2S3(l)
From the overall equation, write the half-equations for the redox process
and label each one as either reduction or oxidation.
5 Name the chemicals that undergo oxidation in the following reactions.
a 2Zn(s) + O2(g) → 2ZnO(s)
b Ca(s) + Cl2(g) → CaCl2(s)
c 2AgBr(s) → 2Ag(s) + Br2(g)
6 Identify each oxidising and reducing agent in Question 5.
7 Metal M is found to react with oxygen to form the compound M2O3.
In a separate reaction, metal M reacted with an aqueous solution of silver
nitrate (AgNO3). The unbalanced and incomplete equations for the reaction
between metal M and AgNO3 are given below.
Ag+(aq) + _____ → Ag(s)
M(s) → ______(aq) + ___e–
M(s) + _____(aq) → _____(aq) + ____Ag(s)
a Complete the half-equations and the overall equation for the reaction
between metal M and silver ions, Ag+(aq).
b Identify each half-equation as either reduction or oxidation.
c Identify the oxidising and reducing agents for the reaction.

106 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
4.2 Oxidation numbers
In this section, you will learn the set of rules that chemists have devised to allow a
wider range of reactions to be classified as redox reactions. This involves assigning
oxidation numbers to the atoms in a reaction.
You will see how oxidation numbers can be used to determine whether a reaction
that does not involve the formation of ions could be classified as a redox reaction
and which substances in a redox reaction have been oxidised or reduced.
You will also discover that many transition metals have multiple oxidation states
and that many of these compounds can be coloured, such as in the reaction shown
in Figure 4.2.1

OXIDATION NUMBERS
In section 4.1 you looked at redox reactions that involved the production of ionic
compounds from their elements. In these cases, it was relatively easy to deduce
which element gained or lost electrons by considering the charge on the ions
produced in the reaction. A species that was reduced gained electrons, becoming
less positive, whereas the oxidised species lost electrons, becoming more positive.
For some redox reactions, it is harder to identify the species that are oxidised
and reduced. For example, the reaction that occurs during the wet corrosion of iron
metal can be represented by the half-equations:
Fe(s) → Fe2+(aq) + 2e–
O2(g) + 2H2O(l) + 4e– → 4OH–(aq) FIGURE 4.2.1 Many redox reactions involve
The first half-equation shows that the iron loses electrons and is oxidised. The colour changes. It is convenient to assign
second half-equation represents a reduction reaction because electrons have been individual oxidation numbers to the atoms
gained. However, it is not obvious if oxygen or hydrogen has gained these electrons.
It is possible to determine which element has been oxidised and which has been
reduced in this reaction by looking at oxidation numbers. Oxidation numbers are
also called oxidation states.
Oxidation numbers have no physical meaning—they do not indicate a formal
charge or the physical or chemical properties of the substance. However, they are a
useful tool for identifying which atoms have been oxidised and which atoms have
been reduced.

Oxidation number rules


Oxidation numbers are assigned to elements involved in a reaction by following
a specific set of rules. In applying these rules, we regard all compounds and
polyatomic ions as though they are composed of individual ions.
Table 4.2.1 (on page 108) describes the rules for determining oxidation
numbers. In the examples, the oxidation number of an element is placed above
its symbol. The plus or minus sign precedes the number and so distinguishes the
oxidation number from the charge on an ion where the sign is generally placed after
the number. For example, the oxide ion (O2–) has a charge of 2– and an oxidation
number of –2. While the values are the same in this instance, it is important to
remember that oxidation states do not always indicate a charge on the species.

CHAPTER 4 | REDOX REACTIONS 107


TABLE 4.2.1

Rule Examples

1 The oxidation number of a free 0 0 0 0


element is zero. Na, C, Cl2, P4

2 The oxidation number of a +1 –1 +2 –2 +3 –3


simple ion is equal to the charge Na+, Cl–, Mg2+, O2–, Al3+, N3–
on the ion.

3 In compounds, some elements


have oxidation numbers that are
regarded as fixed, except in a few
exceptional circumstances. +1 +2
(a) Main group metals have an Ionic compounds: KCl, MgSO4
oxidation number equal to the
charge on their ions. +1
(b) Hydrogen has an oxidation Compounds of H: H2O
number of +1 when it forms
compounds with non-metals. –1 –1
Exception: In metal hydrides Metal hydrides: NaH, CaH2
the oxidation number of
hydrogen is –1. –2
(c) Oxygen usually has an Compounds of O: H2O
oxidation number of –2.
Exceptions:
In compounds with fluorine,
oxygen has a positive
oxidation number. –1 –1
In peroxides, oxygen has an Peroxides: H2O2, BaO2
oxidation number of –1.

4 The sum of the oxidation +4–2


numbers in a neutral compound CO2
is zero. Note that in CO2, the oxidation number of each
oxygen atom is written as –2. It is not written as –4
for two O atoms.

5 The sum of the oxidation +6 –2 –3+1


numbers in a polyatomic ion is SO42–, NH4+
equal to the charge on the ion.

6 The most electronegative +2 –1


element is assigned the negative OF2
oxidation number.

Common oxidation states of the first 36 elements in their compounds are shown
in the periodic table in Figure 4.2.2. Transition metals and some non-metals can
have a range of oxidation states, these are usually calculated after applying the rules
for all other elements in the compound.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1 2
H He
hydrogen +1 oxidation state −1 oxidation state helium

3 4 5 6 7 8 9 10
+2 oxidation state −2 oxidation state
Li Be B C* N* O F Ne
lithium beryllium +3 oxidation state range of oxidation boron carbon nitrogen oxygen uorine neon

11 12 states possible 13 14 15 16 17 18
Na Mg Al Si* P* S* Cl* Ar
sodium magnesium aluminium silicon phosphorus sulfur chlorine argon

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V* Cr* Mn* Fe Co Ni Cu Zn Ga Ge* As* Se* Br* Kr
potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton

FIGURE 4.2.2 Part of the periodic table showing the most common oxidation states of some
elements.

108 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Calculating oxidation numbers
For a compound containing several elements, you can use algebra and the rules
given in Table 4.2.1 to calculate the oxidation number of an element.
For example, to find the oxidation number of sulfur in H2SO4, there is a rule
for hydrogen and for oxygen, which leaves sulfur as the only unknown. If you let
the oxidation number of S equal x, the following expression can be written to solve
for x:
(2 × +1) + x + (4 × –2) = 0
2 + x – 8 = 0
x–6=0
x = +6
You will learn later on in this section how to use oxidation numbers to determine
if a substance has been oxidised or reduced.

Worked example 4.2.1


CALCULATING OXIDATION NUMBERS

Use the rules in Table 4.2.1 to determine the oxidation number of each element
in KClO4.

Thinking Working

Identify an element that has a K is a main group metal in group 1.


set value. Applying rule 3a, the oxidation number
of potassium is +1.

Identify any other elements that have According to rule 3c, oxygen has an
set values. oxidation number of –2 unless attached
to fluorine or in a peroxide.

Use algebra to work out the oxidation Let the oxidation number of chlorine in
number of other elements. KClO4 be x.
Solve the sum of the oxidation numbers
for x:
+1 + x + (4 × –2) = 0
+1 + x – 8 = 0
x–7=0
x = +7

Write oxidation numbers above the +1+7 –2


KClO4
elements in the formula.
Note that the oxidation number of
oxygen is written as –2 (not as –8), even
though there are four oxygen atoms in
the formula.

Worked example: Try yourself 4.2.1


CALCULATING OXIDATION NUMBERS

Use the rules in Table 4.2.1 to determine the oxidation number of each element
in NaNO3.

CHAPTER 4 | REDOX REACTIONS 109


USING OXIDATION NUMBERS
Using oxidation numbers to name chemicals
You may recall from Unit 1 Chemistry that transition elements can form ions
with a number of different charges. This means that many transition metals have
variable oxidation numbers. For example, there are two compounds that can be
called iron chloride: FeCl2 and FeCl3.
Using the rules in Table 4.2.1 (on page 108), you can see that the chloride ion
has an oxidation number of –1. In FeCl2 this means the oxidation number of iron
is +2, whereas in FeCl3 the oxidation number is +3.
To distinguish between the two iron chlorides, insert Roman numerals
representing the appropriate oxidation number in the name.
• FeCl2 is named iron(II) chloride.
• FeCl3 is named iron(III) chloride.
When naming non-metal compounds, you can also use Roman numerals to
show the oxidation number of an element such as nitrogen that has several possible
oxidation states. Nitrogen dioxide (NO2) is called nitrogen(IV) oxide, while nitric
oxide (NO) is nitrogen(II) oxide. This method of naming makes it much easier to
determine the formula from the name of the oxide.

CHEMFILE
Colourful oxidation states
A characteristic property of the transition elements is that they form brightly coloured
compounds. Different oxidation states can result in different colours for the same
transition metal.
Vanadium is a very colourful transition element that has a wide variety of colours
depending on its oxidation state. You can see this in Figure 4.2.3. When its oxidation state
is +5, vanadium is yellow; when its oxidation state is +4, it is light blue; when its oxidation
state is +3, it is green; and when its oxidation state is +2, it is magenta.

FIGURE 4.2.3 These colourful solutions have


been made by adding a reducing agent
(mercury–zinc amalgam) to a yellow solution
containing vanadium(V) ions. The amalgam
reduces the oxidation state of the vanadium
by one each time it is shaken, producing, in
order: blue (+4), green (+3) and magenta (+2)
solutions.

You can use the concept of oxidation numbers to extend the definition of oxidation
and reduction.
In this new definition, a change in oxidation numbers indicates that a redox
reaction has taken place. This can be used as an alternative definition of oxidation
and reduction instead of our earlier definition involving loss and gain of electrons.
It is particularly useful for non-ionic compounds when it is difficult to determine
whether electrons have been transferred.
It can now be stated that:
• oxidation involves an increase in oxidation number
• reduction involves a decrease in oxidation number.
Remember that oxidation and reduction always occur together in a redox
reaction. One process cannot happen without the other.
110 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
If there is no change of oxidation number for all elements in a reaction, then the
reaction is not a redox reaction.
Oxidation numbers can be used to analyse the equation of a reaction and
determine whether it represents a redox process.
At the beginning of this chapter, you were alerted to a number of everyday
processes that are redox reactions. Combustion reactions, where fuel is burned
in order to produce heat while giving off CO2 and water, are examples of redox
reactions that are very important in our society. The equation for the burning of
carbon in excess oxygen is:
C(s) + O2(g) → CO2(g)
At first glance, the reaction may not seem like a redox reaction because none of
the species are ionic compounds so it is not clear which reactant is losing or gaining
electrons. Using oxidation numbers though, you can identify both an oxidation
process and a reduction process for the reaction.
0 0 +4 –2
C(s) + O2(g) → CO2(g)
The carbon is oxidised because its oxidation number increases from 0 to +4 and
the oxygen is reduced because its oxidation number decreases from 0 to –2.
The use of oxidation numbers allows you to look at a chemical reaction and
determine whether it is a redox process.

Worked example 4.2.2


USING OXIDATION NUMBERS TO IDENTIFY OXIDATION AND REDUCTION
IN AN EQUATION

Use oxidation numbers to determine which element has been oxidised and
which has been reduced in the following equation:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

Thinking Working

Determine the oxidation Choose C as the first element.


numbers of one of the –4 +4
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
elements on each side of
the equation.

Assess if the oxidation number The oxidation number of C has increased


has changed. If so, identify if from –4 to +4, so carbon in CH4 has been
it has increased (oxidation) or oxidised.
decreased (reduction).

Determine the oxidation Choose oxygen as the second element.


numbers of a second element 0 –2 –2
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
on the left-hand and the
right-hand side of the equation.

Assess if the oxidation number The oxidation number of O has decreased


has changed. If so, identify if from 0 to –2, so O2 has been reduced.
it has increased (oxidation) or
decreased (reduction).

Continue this process until Determine the oxidation numbers


the oxidation numbers of of hydrogen.
all elements have been +1 +1
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
determined.
The oxidation number of H has not changed.

CHAPTER 4 | REDOX REACTIONS 111


Worked example: Try yourself 4.2.2
USING OXIDATION NUMBERS TO IDENTIFY OXIDATION AND REDUCTION
IN AN EQUATION

Use oxidation numbers to determine which element has been oxidised and
which has been reduced in the following equation:
CuO(s) + H2(g) → Cu(s) + H2O(l)

Using oxidation numbers to identify conjugate redox pairs


When a half-equation is written for an oxidation reaction, the reactant, a reducing
agent, loses electrons. The product is an oxidising agent. We refer to the reactant
and the product that it forms as a conjugate redox pair.
For example, in the half-equation for the oxidation of zinc:
Zn(s) → Zn2+(aq) + 2e–
zinc metal (Zn) is a reducing agent and it forms Zn2+(aq), an oxidising agent. Zn(s)
and Zn2+(aq) form a conjugate redox pair Zn(s)/Zn2+(aq).
In the Zn(s)/Zn2+(aq) conjugate redox pair, the oxidation number of zinc
increases from 0 to +2. The increase in the oxidation number of zinc indicates that
it is an oxidation half-reaction.
For the reduction half-equation, the reactant is an oxidising agent and will gain
electrons. The product formed is a reducing agent. Therefore, another conjugate
redox pair is present in the redox reaction.
For example, consider the half-equation for the reduction of Ag+(aq):
Ag+(aq) + e– → Ag(s)
Ag (aq) is an oxidising agent and forms Ag(s), which is a reducing agent. Ag+(aq)
+

and Ag(s) are also a conjugate redox pair. In this case, the oxidation number of
silver decreases from +1 to 0, indicating that this is a reduction half-equation.
The relationship between changes in oxidation numbers and conjugate redox
pairs can be seen by following the colour-coding in the equation in Figure 4.2.4.
One conjugate redox pair is red and the other one is blue.
conjugate
redox pair
oxidation
number
0 +1 +2 0
Zn(s) 2Ag+(aq) Zn2+(aq) 2Ag(s)
+ → +
reducing oxidising conjugate conjugate
agent agent oxidising agent reducing agent

conjugate
redox pair

FIGURE 4.2.4 The change in oxidation numbers seen in conjugate redox pairs. For each redox
reaction, there are two conjugate redox pairs.

112 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
4.2 Review
SUMMARY

• Oxidation numbers are calculated according to a • For oxidation to occur, there must be a
set of rules. corresponding reduction.
– Free elements have an oxidation number of 0. • If there is no change in the oxidation number of all
– In ionic compounds composed of simple ions, elements in the equation for a reaction, then the
the oxidation number is equal to the charge on reaction is not a redox reaction.
the ion. • A conjugate redox pair consists of an oxidising agent
– Oxygen in a compound usually has an oxidation (a reactant) and the reducing agent (a product) that
number of –2. is formed when the oxidising agent gains electrons.
– Hydrogen in a compound usually has an In this case, the oxidation number of the oxidising
oxidation number of +1. agent decreases.
– The sum of the oxidation numbers in a neutral The other conjugate redox pair in a redox reaction
compound is 0. is made up of a reducing agent (a reactant) and
– The sum of the oxidation numbers in a the oxidising agent (a product) that is formed when
polyatomic ion is equal to the charge on the ion. the reducing agent loses electrons. In this case, the
oxidation number of the reducing agent increases.
• Transition metals and some non-metals have
variable oxidation numbers that can be calculated • Figure 4.2.5 summarises the redox terms that
using the rules above. you need to understand from this section. This
information is built up from the basic principles of
• An increase in the oxidation number of an element
redox that were introduced in Heinemann Chemistry 1,
in a reaction indicates oxidation has occurred.
Chapter 16.
• A decrease in the oxidation number of an element
in a reaction indicates reduction has occurred.
oxidation number oxidation number
increases decreases

e–
reducing oxidising
agent agent

Reducing agent Oxidising agent


– loses electrons – accepts electrons
– reduces the oxidising agent – oxidises the reducing agent
– undergoes oxidation – undergoes reduction
– is the reactant in the oxidation – is the reactant in the reduction
half-reaction: half-reaction:
reducing agent oxidising agent + ne–

conjugate oxidised form + ne– conjugate reduced form

FIGURE 4.2.5 Summary of redox reaction terms.

CHAPTER 4 | REDOX REACTIONS 113


KEY QUESTIONS

1 State the oxidation number of carbon in:


a CO
b CO2
c CH4
d C (graphite)
e HCO3–
2 Which one or more of the following substances contain manganese in the
+6 oxidation state: MnCl2, MnCl3, MnO2, K2MnO4, KMnO4?
3 Find the oxidation numbers of each element in the following compounds
or ions. Hint: For ionic compounds, use the charge on each ion to help you.
a CaO
b CaCl2
c HSO4–
d MnO4–
e F2
f SO32–
g NaNO3
h K2Cr2O7
4 Assign oxidation numbers to each element in these equations, and hence
identify the oxidising agents and reducing agents.
a Mg(s) + Cl2(g) → MgCl2(s)
b 2SO2(g) + O2(g) → 2SO3(g)
c Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
d 2Fe2+(aq) + H2O2(aq) + 2H+(aq) → 2Fe3+(aq) + 2H2O(l)
5 For each of the following redox reactions, complete the table to show the
conjugate redox pairs.

Redox reaction Conjugate redox Conjugate redox


pair (oxidation pair (reduction
process) process)

Na(s) + Ag+(aq) → Na+(aq) + Ag(s)

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

2K(s) + Cl2(g) → 2K+(s) + 2Cl–(s)

114 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
4.3 Writing complex redox equations
Not all oxidation and reduction half-equations involve simple ions and their
elements. Many interesting redox reactions, such as the iodine clock reaction shown
in Figure 4.3.1, involve reactants and products that have oxygen and hydrogen in
their formulas. In this section, you will learn how to balance more complex half-
equations in a few simple steps.

FIGURE 4.3.1 This redox reaction involving colour changes is known as a clock reaction. The black
compound is a starch–iodine complex.

BALANCING OXYGEN AND HYDROGEN IN


HALF-EQUATIONS
Half-equations that involve atoms or simple ions can be written quite easily.
For  example, knowing that magnesium metal is oxidised to form Mg2+ ions in
solution, you can readily write the half-equation as:
Mg(s) → Mg2+(aq) + 2e–
However, half-equations involving polyatomic ions are usually less obvious.
The  anaesthetic nitrous oxide or laughing gas (N2O) can be prepared by the
reduction of nitrate ions in an acidic solution:
2NO3–(aq) + 10H+(aq) + 8e– → N2O(g) + 5H2O(l)
Such equations can be deduced from the following steps. The reduction of
nitrate ions will be used to illustrate this process.
1 Balance all elements except hydrogen and oxygen in the half-equation.
2NO3– → N2O
2 Balance the oxygen atoms by adding water molecules.
2NO3– → N2O + 5H2O
3 Balance the hydrogen atoms by adding H+ ions (which are present in acidic
solution).
2NO3– + 10H+ → N2O + 5H2O
4 Balance the charge in the equation by adding electrons.
In this case, the total charge on the left-hand side is (2 × –1) + (10 × +1) = +8.
The total charge on the right-hand side is 0. Make the charges equal by adding
8 electrons to the left-hand side.
2NO3– + 10H+ + 8e– → N2O + 5H2O
5 Add states to complete the half-equation.
2NO3–(aq) + 10H+(aq) + 8e– → N2O(g) + 5H2O(l)

CHAPTER 4 | REDOX REACTIONS 115


When writing half- and overall equations, it is important that they are fully
balanced (Figure 4.3.2). The number of each element must be equal on each side,
just as with any other chemical equation. The charge for each side of the equation
must also be equal. It is important to remember that the charges being equal does
not mean they must be zero.

Reactants Produ
cts
Charge Charge

FIGURE 4.3.2 In balanced half- and overall equations, the number of atoms of each element is equal

Worked Example 4.3.1 shows how to balance a complex redox half-equation.


The final equation in this example has an overall charge of +6 for each side.

Worked example 4.3.1


BALANCING A HALF-EQUATION IN ACIDIC SOLUTION

Write the half-equation for the reduction of an acidified solution of Cr2O72– to


aqueous Cr3+.

Thinking Working

Balance all elements There are 2 Cr atoms in Cr2O72–, so 2 Cr atoms are


except hydrogen and needed on the right-hand side (RHS).
oxygen in the half- Cr2O72– → 2Cr3+
equation.

Balance the oxygen There are 7 O atoms in Cr2O72–, so 7 H2O molecules are
atoms by adding added to the RHS.
water. Cr2O72– → 2Cr3+ + 7H2O

Balance the There are now 14 H atoms on the RHS and none on
hydrogen atoms by the left-hand side (LHS), so 14 H+ ions are added to
adding H+ ions. the LHS.
Acids provide a Cr2O72– + 14H+ → 2Cr3+ + 7H2O
source of H+ ions.

Balance the charge The charge on the LHS is (–2) + (+14) = +12 and on
in the equation by the RHS is 2 × +3 = +6, so 6 electrons are added to the
adding electrons. LHS to make the charges equal.
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O

Add states to All states are (aq) except for water, which is (l).
complete the half- Cr2O72–(aq) + 14H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l)
equation.

116 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
BALANCING A HALF-EQUATION IN ACIDIC SOLUTION

Write the half-equation for the reduction of an acidified solution of MnO4– to


solid MnO2.

CHEMFILE
Vinegary wine or winey vinegar?
The oxidation of ethanol forms ethanoic acid. Ethanoic acid is the main ingredient
of vinegar and is responsible for its sourness. If a bottle of wine is left open to the

This reaction is put to good use when specialist vinegars such as apple cider vinegar,
red wine vinegar and even beer vinegar (Figure 4.3.3) are made by deliberately
oxidising the appropriate alcoholic beverage under the right conditions.
The oxidation half-equation for the production of ethanoic acid from ethanol is given by:
FIGURE 4.3.3 A selection of vinegars.
C2H5OH(aq) + H2O(l) → CH3COOH(aq) + 4H+(aq) + 4e–
vinegar, white wine vinegar and malt vinegar.

EXTENSION

Balancing half-equations under alkaline conditions


If a redox reaction occurs in an alkaline environment, 2 Balance the hydrogen atoms by adding H+ ions.
OH– rather than H+ can be used to balance the equation. O2(g) + 4H+(aq) → 2H2O(l)
The steps are very similar to balancing redox processes 3 Balance the charge by adding electrons.
under acidic conditions as outlined below. O2(g) + 4H+(aq) + 4e– → 2H2O(l)
Consider the oxidation of cadmium, Cd(s), to Cd(OH)2(s) 4 Add enough hydroxide ions to both sides of the equation
in alkaline solution. to neutralise the H+ ions on the left-hand side of
1 Balance all elements except hydrogen and oxygen in the equation.
the half-equation. O2(g) + 4H+(aq) + 4OH–(aq) + 4e– → 2H2O(l) + 4OH–(aq)
Cd(s) → Cd(OH)2(s) 5 The neutralisation reaction between H+(aq) and OH–(aq)
2 Balance the hydroxide ions by adding OH–(aq) on the produces water, so cancel out the water molecules on
left-hand side of the equation. the side where there are less water molecules.
2
Cd(s) + 2OH–(aq) → Cd(OH)2(s) O2(g) + 4H2O(l) + 4e– → 2H2O(l) + 4OH–(aq)
3 Balance the charge by adding electrons on the right- O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
hand side of the equation. While you will not see many examples of balancing
Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e– under alkaline conditions during your study of Units 3
Sometimes it is not obvious where the hydroxide ions and 4 Chemistry, you will probably have made use of
should be placed; for example, in the reduction of oxygen these reactions many times in your daily life. For example,
to form water. In this case, you can balance the half- the redox process that generates electricity in a common
equation as though it occurs in acidic solution, then add alkaline battery is maintained through alkaline conditions
hydroxide ions later. Follow the steps below to see how this rather than acidic conditions.
is done.
1 Balance the oxygen atoms by adding water.
O2(g) → 2H2O(l)

CHAPTER 4 | REDOX REACTIONS 117


OVERALL REDOX EQUATIONS UNDER ACIDIC CONDITIONS
To write an overall redox equation, you add the oxidation half-equation to the
reduction half-equation, making sure that the number of electrons used in reduction
equals the number of electrons released during oxidation. In addition, for redox
reactions under acidic conditions, H+ ions and H2O molecules are also present as
reactants and products, which will need to be cancelled down.

Worked example 4.3.2


COMBINING HALF-EQUATIONS TO WRITE OVERALL REDOX EQUATIONS
UNDER ACIDIC CONDITIONS

Write balanced oxidation and reduction half-equations for the reaction in which C2H5OH(aq) and Cr2O72–(aq) react to form
CH3COOH(aq) and Cr3+(aq). Then write the overall redox equation for the reaction.

Thinking Working

Identify one reactant and the product it forms, and write C2H5OH(aq) + H2O(l) → CH3COOH(aq) + 4H+(aq) + 4e–
the balanced half-equation.

Identify the second reactant and the product it forms, and Cr2O72–(aq) + 14H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l)
write the balanced half-equation.

Multiply one or both equation(s) by a suitable factor to Lowest common multiple = 12
ensure that the number of electrons on both sides of the 3 × [C2H5OH(aq) + H2O(l) → CH3COOH(aq) + 4H+(aq) + 4e–]
arrow is equal.
2 × [Cr2O72–(aq) + 14H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l)]
3C2H5OH(aq) + 3H2O(l) → 3CH3COOH(aq) + 12H+(aq) + 12e–
2Cr2O72–(aq) + 28H+(aq) + 12e– → 4Cr3+(aq) + 14H2O(l)

Add the oxidation and the reduction half-equations 3C2H5OH(aq) + 3H2O(l) → 3CH3COOH(aq) + 12H+(aq) + 12e–
together, cancelling electrons so that none appear in the 16H+ 11H20
final equation. 2Cr2O72–(aq) + 28H+(aq) + 12e– → 4Cr3+(aq) + 14H2O(l)
Also cancel H2O and H+ if these occur on both sides 3C2H5OH(aq) + 2Cr2O72–(aq) + 16H+(aq) →
of the arrow. 3CH3COOH(aq) + 4Cr3+(aq) + 11H2O(l)

COMBINING HALF-EQUATIONS TO WRITE OVERALL REDOX EQUATIONS


UNDER ACIDIC CONDITIONS

Write balanced oxidation and reduction half-equations for the reaction in which
SO32–(aq) and ClO–(aq) react to form H2S(g) and ClO3–(aq). Then write the overall
equation for the reaction.

Some strong oxidising agents such as potassium dichromate are highly coloured.
The change in colour that occurs as the redox process proceeds can be used for a
number of chemical analyses.
FIGURE 4.3.4 The oxidation of ethanol, The reaction of an alcohol with acidified dichromate as seen in Worked Example
described in Worked Example 4.3.2, was the 4.3.2 can be followed by the colour change of the solution from orange to green
basis of an older form of the breathalyser.
(Figure 4.3.4). This colour change was the basis for older form of handheld
The presence of alcohol in a motorist’s breath
breathalysers used for testing the blood alcohol level of drivers.
oxidising agent, potassium dichromate. During
the reaction, the yellow-orange colour of
dichromate ions changed to the green colour of

118 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHEMISTRY IN ACTION

Alcohol and the road toll


Drinks such as wine, beer, vodka and bourbon contain Regulations require that the ethanol content of alcoholic
ethanol (CH3CH2OH). Ethanol acts as a depressant, slowing drinks be specified on their labels, since the content
the functioning of the brain. When alcoholic drinks are determines how much drink can be consumed without
consumed in excess, their intoxicating qualities can lead adverse effects.
to antisocial behaviour and can damage a person’s health. Because ethanol slows down reaction time, it seriously
The ethanol content of alcoholic drinks varies, as shown affects a person’s driving skills. It is estimated that alcohol
in Table 4.3.1. has contributed to nearly 40% of all road accidents.
Governments have responded by introducing penalties,
TABLE 4.3.1 Typical ethanol contents of selected alcoholic beverages such as fines and licence disqualification, for drivers whose
blood alcohol concentration exceeds a certain level—
Drink Ethanol content
(%v/v) typically 0.05%(m/v). Probationary or P-plate drivers are
required to have a zero blood alcohol level.
Spirits (brandy, bourbon, gin, rum, vodka 37
whiskey etc.) The introduction of penalties, a policy of randomly
testing motorists for blood alcohol level, and various
Port, sherry 18
advertising campaigns have all helped to increase public
Wines (including sparkling wines) 12 awareness of the link between alcohol consumption and
Alcoholic cider 10 road accidents. Figure 4.3.5 shows how the road toll in
Victoria changed during the period when these various
Beer 5.0
measures designed to discourage drink driving were
‘Light’ beer 2.5 introduced.
Pre-mixed vodka-based drinks 9

10
0.05% law
introduced
9

8
Fatality rate per 10 000 vehicles

5 zero blood
increased alcohol for
blood alcohol probationary
3 km/h tolerance
4 penalties drivers
on speeding replaces
10% tolerance
50 km/h limit in
random residential areas
3 breath-testing introduced
introduced 40 km/h around
2 schools
increased
penalties
1

1962 1966 1970 1974 1978 1982 1986 1990 1994 1998 2002 2006 2010 2014
Year
FIGURE 4.3.5 Deaths on Victorian roads 1960–2015. Continual improvements and action on road safety, including crackdowns on drink-driving,

CHAPTER 4 | REDOX REACTIONS 119


FIGURE 4.3.6

Chemists were involved in the invention of the The blood alcohol content may then be confirmed by
breathalyser, an instrument designed for police to use to instrumental techniques such as infrared spectroscopy or
estimate blood alcohol content (Figure 4.3.6). Rather than gas–liquid chromatography. Some police departments also
analysing samples of blood, this instrument measures use alcohol fuel cell sensors.
the concentration of alcohol in a person’s breath, which The first breathalysers operated by detecting the colour
is closely related to the concentration of alcohol in change that occurs when ethanol reacts with an acidified
their blood. solution of potassium dichromate (K2Cr2O7), forming
If this screening test indicates that a driver’s blood Cr3+ ions and ethanoic acid. The redox reaction can be
is over 0.05%(m/v), more accurate measurements represented by the equation:
are taken either in a ‘booze bus’ or at a police station.
2Cr2O72–(aq) + 3CH3CH2OH(g) + 16H+(aq) → 4Cr3+(aq) + 3CH3COOH(aq) + 11H2O(l)
orange green

CHEMFILE
Elephant’s toothpaste
Hydrogen peroxide is such a strong oxidising agent that it can

H2O2(aq) + H2O2(aq) → 2H2O(l) + O2(g)

H2O2(aq) + 2H+(aq) + 2e– → 2H2O(l)


H2O2(aq) → O2(g) + 2H+(aq) + 2e–
The decomposition reaction of hydrogen peroxide is the basis
for the impressive ‘foam column’ or ‘elephant’s toothpaste’
demonstration that is commonly shown by chemistry teachers FIGURE 4.3.7 The ‘elephant’s toothpaste’ demonstration involves a
redox reaction in which hydrogen peroxide reacts with itself to form
water and oxygen gas. In this reaction, the hydrogen peroxide is
When detergent and a catalyst are added to concentrated both the reducing agent and the oxidising agent. In this image, solid
hydrogen peroxide solution, a column of foam is formed potassium iodide catalyst is added to hydrogen peroxide solution.

120 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
4.3 Review
SUMMARY

• To balance redox half-equations under acidic • To write an overall equation, add the oxidation
conditions: half-equation and the reduction half-equation,
1 Balance all atoms except hydrogen and oxygen. making sure that the number of electrons used in
2 Balance the oxygen atoms by adding water reduction equals the number of electrons released
molecules. during oxidation.
3 Balance the hydrogen atoms by adding H+ ions. • When combining oxidation and reduction half-
4 Balance the charge by adding electrons. equations under acidic conditions, any H+(aq)
and H2O(l) that appear on both sides of the arrow
5 Add states.
should be cancelled down.

KEY QUESTIONS

1 Write half-equations for the:


a reduction of MnO2 to Mn2+
b reduction of MnO4– to MnO2
c reduction of SO42– to H2S
d oxidation of SO2 to SO42–
e oxidation of H2S to S
f oxidation of SO32– to SO42–.
2 When zinc powder is sprinkled into an acidified solution of potassium
dichromate, a reaction occurs that produces zinc ions and chromium(III)
ions in solution.
a Write the oxidation half-equation for the reaction.
b Write the reduction half-equation for the reaction.
c Use your answers to parts a and b to write a balanced equation for the
overall reaction.
3 Write the half-equations and the balanced overall equation for the reaction
in which:
a a solution containing iron(II) ions is oxidised by an acidified solution
containing dichromate ions (Cr2O72–). The products include iron(III) and
chromium(III) ions
b a solution containing sulfite ions (SO32–) reacts with an acidified
solution of permanganate ions (MnO4–) to produce a colourless solution
containing sulfate ions and manganese(II) ions
c manganese dioxide (MnO2) reacts with concentrated hydrochloric acid
to form chlorine gas and a solution containing manganese(II) ions.
4 The following equations are not balanced.
i Identify the species that has been reduced and the species that
has been oxidised.
ii Write balanced half-equations for the oxidation and reduction
reactions.
iii Combine the half-equations to write a balanced overall equation.
a Ce4+(aq) + H2S(g) → Ce3+(aq) + S(s) + H+(aq)
b NO3–(aq) + H+(aq) + Cu(s) → NO(g) + H2O(l) + Cu2+(aq)
c H2O2(aq) + Br–(aq) + H+(aq) → Br2(l) + H2O(l)
d MnO2(s) + H+(aq) + S(s) → Mn2+(aq) + H2O(l) + SO2(g)

CHAPTER 4 | REDOX REACTIONS 121


Chapter review
KEY TERMS

conjugate redox pair oxidation number reduced


half-equation oxidised reducing agent
main group metal oxidising agent reduction
oxidation redox reaction transition element

Oxidation and reduction 6 Identify the reducing agent in each of these redox
1 State whether each of the statements are true or false. reactions.
a Group 1 and 2 metal ions, such as Na+, are a 2Cu(s) + O2(g) → 2CuO(s)
reducing agents because they tend to lose b Mg(s) + Cl2(g) → MgCl2(s)
electrons. c 2Fe3+(aq) + Zn(s) → Zn2+(aq) + 2Fe2+(aq)
b Group 17 molecules, such as I2, can be oxidising d 2Ag+(aq) + Ni(s) → Ni2+(aq) + 2Ag(s)
agents or reducing agents.
Oxidation numbers
c Non-metal ions, such as Cl–, can be reducing agents
7 What is the oxidation number of sulfur in each of
because they can lose electrons.
the following compounds?
d Metals, such as Cu, can be oxidising agents because
a SO2
they can gain electrons.
b H2S
2 Complete the following sentences, which describe
c H2SO4
oxidation and reduction.
d SO3
Oxidation and reduction occur together. Oxidation
e Na2SO3
occurs when an atom _____________ electrons to
form a ____________ ion, such as happens when a f Na2S2O3
calcium atom, with an electronic configuration of 8 Complete the following table.
2,8,8,2 _______________ electrons to form a Ca2+ ion. Compound Element Oxidation number
Reduction occurs when an atom _______________
electrons to form a _____________ ion or a cation CaCO3 Ca
___________ electrons to become a neutral atom. An HNO3 O
example is when a bromine atom, with ____________
H2O2 –1
electrons in its valence shell, ___________ an electron
to form a ____________ ion. HCO3− +4

3 Lead metal is oxidised to form Pb2+ ions by reaction HNO3 N


with silver ions in solution. Write half-equations for the –
KMnO4 Mn
reaction and then write the balanced overall equation.
H2S S
4 Classify each of the following half-equations as either
oxidation or reduction half-equations. Cr2O3 Cr
a Mg(s) → Mg2+(aq) + 2e– N2O4 N
b 2Br–(aq) → Br2(aq) + 2e–
c Cu2+(aq) + 2e– → Cu(s) 9 Place the following substances in order of increasing
d K(s) → K+(aq) + e– oxidation states of nitrogen.
e Fe3+(aq) + e– → Fe2+(aq) NO, K3N, N2O4, N2O, Ca(NO3)2, N2O3, N2
f I2(aq) + 2e– → 2I–(aq) 10 Which of the following reactions are redox reactions?
5 Each of the following half-equations have a mistake Give reasons for each of your answers.
in them. For each half-equation state what the error a BaCl2 + H2SO4 → BaSO4 + 2HCl
is and then write the correct half-equation. b 2Ag + Cl2 → 2AgCl
a Ag(s) + e– → Ag+(aq) c 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4
b Cu(s) + e– → Cu2+(aq) + 3e– d ZnCO3 → ZnO + CO2
c Zn(aq) → Zn2+(s) + 2e– e HPO32– + I2 + OH– → H2PO4– + 2I–
d I2(aq) + e– → I–(aq) f 2Cu+ → Cu2+ + Cu
e Na+(aq) – e– → Na(s) g CaF2 → Ca2+ + 2F–
h P4 + 6H2 → 4PH3

122 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
11 Complete the table by determining the oxidation Writing complex redox equations
number of the underlined atom in the compound 14 Complete the summary below as you balance the
or ion. half-equation for the reduction of NO3– to NO2 in
acidic solution.
Species Oxidation number of the underlined atom
NO3–(aq) → NO2(g)
a CuO
Step Task How it’s done Half-
b Fe(OH)3
equation
c HClO2
1 Balance NO3–(aq) →
d MnO4 – nitrogens. NO2(g)

e Cr2O72– 2 Balance Add _____ H2O


oxygens by molecule(s) to
adding _______. right-hand side of
12 Copper bowls and trays can be decorated by etching the equation.
patterns on them using concentrated nitric acid. The
3 Balance Add ______ H+ ion(s)
overall reaction is: hydrogens by to _________ of
Cu(s) + 4HNO3 (aq) → Cu(NO3)2(aq) + 2NO2(g) adding _____. the equation.
+ 2H2O(l)
4 Balance charge Charge on left-hand
a What is the oxidation number of copper: by adding side = ______
i before the reaction? _______. Charge on right-hand
ii after the reaction? side = ______
Add ______ e– to
b What is the oxidation number of nitrogen: the _______ of the
i before the reaction? equation.
ii after the reaction? 5 Add state Give the appropriate
c Name the oxidising agent and reducing agent symbols to give states for each
in this process. the final half reactant and product
equation. in the equation.
13 Complete the following table, giving the conjugate
redox pairs for each of the reactions.
15 The unbalanced half-equation for the reduction of the
Equation Conjugate Conjugate iodate ion (IO3–) is:
redox pair redox pair 2IO3–(aq) + xH+(aq) + ye– → I2(aq) + zH2O(l)
(oxidation) (reduction)
Complete the equation by inserting the correct
Fe(s) + I2(aq) → FeI2(aq) coefficients for x, y and z.
Mg(s) + FeCl2(aq) → MgCl2(aq) 16 When sulfur dioxide is bubbled through an acidified
+ Fe(s) solution of sodium dichromate, sulfate ions and
10Br–(aq) + 2MnO4–(aq) + 16H+(aq) green chromium(III) ions are formed. Write the half-
→ 2Mn2+(aq) + 8H2O(l) + 5Br2(aq) equations for this reaction and then deduce the
balanced overall equation.
Cu(s) + 2NO3–(aq) + 4H+(aq) →
Cu2+(aq) + 2NO2(g) + 2H2O(l) 17 During each of the following analyses, redox reactions
occurred. Write half-equations for the oxidation and
reduction reactions. Use these half-equations to write
an overall equation for each reaction.
a Zinc was analysed by reacting it with a solution of
Pb2+ ions. Lead metal was precipitated and Zn2+
ions were formed.
b The amount of Fe2+ ions in iron tablets was
determined by oxidising them to Fe3+ ions, using
an acidified solution of MnO4– ions. The MnO4– ions
were reduced to Mn2+ ions during the reaction.
c Sulfur(IV) dioxide (SO2), a preservative in dried
fruit, was determined by oxidation to SO42– using
a solution of I2. Iodide (I–) ions were produced.

CHAPTER 4 | REDOX REACTIONS 123


d An acidified solution of bleach, which contains b Write half-equations for the oxidation and reduction
OCl– ions, was titrated against a solution of I– ions. reactions that occur when sodium dithionite is
The reaction products included Cl– and I2. mixed with water.
18 In dry cells commonly used in torches, an electric 22 Solid ammonium dichromate decomposes to form
current is produced from the reaction of zinc metal chromium(III) oxide, nitrogen gas and steam.
with solid MnO2. During this reaction, Zn2+ ions and a Calculate the oxidation numbers of chromium and
solid Mn2O3 are formed. Write half-equations, and nitrogen in the reactant ammonium dichromate
hence an overall equation, for the reaction. ((NH4)2Cr2O7) and the products Cr2O3 and N2.
19 Vitamin C is an essential vitamin to maintain good Identify which reactants have been reduced and
health. The amount of vitamin C present in food can oxidised.
be determined by titration against a solution of iodine, b Complete and balance the following half-equations.
using starch as an indicator. The reaction is a redox i NH4+(s) → N2(g)
process and can be represented by the following ii Cr2O72–(s) → Cr2O3(s)
overall equation: c Identify each of the half-equations in part b as
C6H8O6(aq) + I2(aq) → C6H6O6(aq) + 2H+(aq) + 2I–(aq) either reduction or oxidation processes and explain
a Write the two half-equations for the reaction. your answer in terms of oxidation numbers.
b Identify each reaction as either oxidation d Write the balanced overall equation for the reaction
or reduction. that occurs.
20 Answer the following questions about the reaction of e Identify the conjugate redox pairs for the reaction.
H3AsO4(aq) with I–(aq). The unbalanced equation for 23 The thermite process can be used to weld lengths of
the reaction is: railway track together. A mould placed over the ends
H3AsO4(aq) + I–(aq) → As2O3(s) + IO3–(aq) + H2O(l) of the two rails to be joined is filled with a charge
a Write the two half-equations for the reaction. of aluminium powder and iron(III) oxide. When the
b Write a balanced overall equation using your two mixture is ignited, a redox reaction occurs to form
half-equations from part a. molten iron, which joins the rails together, and
aluminium oxide.
Connecting the main ideas a Write a half-equation for the conversion of iron(III)
21 As a result of a traffic accident, residents in a oxide to metallic iron and oxide ions.
Melbourne suburb had to be evacuated when toxic b Is the half-equation you wrote for part a, an
fumes leaked from a container of sodium dithionite oxidation or a reduction process?
(Na2S2O4). The dithionite ion reacts with water
c Write the overall equation for the thermite process.
according to the equation:
d What mass of iron(III) oxide must be present in the
2S2O42–(aq) + H2O(l) → S2O32–(aq) + 2HSO3–(aq)
charge if each joint requires 3.70 g of iron to weld
a State the oxidation number of the sulfur in the it together?
following ions.
i S2O42–
ii S2O32–
iii HSO3–

124 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHAPTER

Galvanic cells as a source


of energy
By the end of this chapter, you will know how galvanic cells generate electricity
from chemical reactions. You will see how experimental data from galvanic cells
can be used to compare the relative strengths of oxidising and reducing agents.
You will compare an exothermic redox reaction in a test tube with the same redox
reaction where the reactants are in separate half-cells and electron transfer is used
to produce a portable energy source.
The relative strengths of oxidising and reducing agents are conveniently
summarised in a table known as the electrochemical series. You can use the
electrochemical series to predict the likelihood of individual redox reactions
occurring, and to calculate the potential differences of different galvanic cells.
Finally, you will investigate how different types of galvanic cells are used as a
source of power for a range of uses.

Key knowledge
• Redox reactions with reference to electron transfer, reduction and oxidation
reactions, reducing and oxidising agents
• The writing of balanced half-equations for oxidation and reduction reactions
and balanced ionic equations, including states, for overall redox reactions
• Galvanic cells as primary cells and as portable or fixed chemical energy storage
devices that can produce electricity (details of specific cells not required)
including common design features (anode, cathode, electrolytes, salt bridge
and separation of half-cells) and chemical processes (electron and ion flows,
half-equations and overall equations)
• The comparison of the energy transformations occurring in spontaneous
exothermic redox reactions involving direct contact between reactants
(transformation of chemical energy to heat energy) compared with those
occurring when the reactants are separated in galvanic cells (transformation
of chemical energy to electrical energy)
• The use of the electrochemical series in designing and constructing galvanic
cells and as a tool for predicting the products of redox reactions, deducing
overall equations from redox half-equations and determining maximum cell
voltage under standard conditions
• The operation of rechargeable batteries (secondary cells) with reference to
discharging as a galvanic cell and recharging as an electrolytic cell, including
the redox principles (redox reactions and polarity of electrodes) and the factors
affecting battery life with reference to components and temperature (no specific
battery is required)

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


5.1 Galvanic cells
Electronic devices such as mobile phones, notebook computers, cameras and
hearing aids all depend on small portable sources of electricity: cells and batteries
(see Figure 5.1.1). Portable energy in the form of cells and batteries enables you to
operate electrical equipment without the restrictions of a power cord.
The demand for electronic devices has stimulated the production of a variety of
cells, from tiny button cells for watches and calculators, to the huge batteries used
to operate lighthouses. The energy provided by cells and batteries may be more
expensive than energy from other sources, such as fossil fuels, but this cost is offset
FIGURE 5.1.1 Your way of life depends on cells by their convenience.
In this section, you will find out how cells are constructed, and how they provide
you with a source of electrical energy.

CHEMISTRY IN ACTION

A technological leap beginning with


a frog’s leap
The history of electrochemistry began in 1791 when Italian biologist Luigi
Galvani and his assistant were experimenting with dissected frogs. They were
startled to see a frog’s leg hanging on a copper hook twitch when it touched
an iron rail. The muscles of the frog were stimulated by an electric shock.
Galvani had just discovered how to generate a current. His ‘error’ was in
thinking that the current was some sort of life force, a perfectly reasonable
idea for the time.
Other scientists set out to investigate the possibility that metals were
involved in this phenomenon. After several years’ work, in 1800, Alessandro
FIGURE 5.1.2 Volta developed a device that used a chemical reaction to produce an electric
current. Figure 5.1.2 shows the device, now called a ‘voltaic pile’. It consisted
of a stack of alternating copper and zinc discs separated by cardboard soaked
in salt water.

INTRODUCING GALVANIC CELLS


An electrochemical cell is a device in which chemical energy is converted into
electrical energy, or vice versa. A galvanic cell (which is also known as a voltaic
cell) is a type of electrochemical cell in which chemical energy is converted into
electrical energy. The cells in your mobile phone and laptop are galvanic cells.
If we connect several cells in series to obtain a higher potential difference or
‘voltage’, the combination of cells is called a battery. The term ‘battery’ strictly
only applies to a combination of cells, but it is in everyday use to describe cells
as well.
Figure 5.1.3 shows how you can produce a galvanic cell from simple laboratory
equipment.
In Figure 5.1.4, you can see a diagram of a cell called the Daniell cell, named
after the scientist who invented it in 1836, John Daniell. The cell produces an
electric current that flows through the wire and light globe. This part of the cell is
FIGURE 5.1.3
called the external circuit. The globe converts the electrical energy of the current
into light and heat.

126 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
low-power
light globe

salt bridge: a strip of

potassium nitrate solution


zinc electrode copper
electrode

zinc sulfate solution copper(II)


sulfate solution

FIGURE 5.1.4

The current flows because a chemical reaction is taking place in the cell. If you
leave the cell with a light globe connected for several hours, you will see evidence of
this reaction occurring: the zinc metal corrodes, the copper metal becomes covered
with a furry dark brown deposit and the blue copper(II) sulfate solution loses some
of its colour.

CHEMFILE
The Daniell cell
In 1836, English chemist John Daniell invented a device that could supply a useful
electric current. The device, which became known as the Daniell cell, was used almost
exclusively to power the early English and US telegraph systems because of its reliable
output.

If you replace the light globe with a galvanometer (an instrument for detecting
electric current), the galvanometer will indicate that electrons flow from the zinc
electrode through the wire to the copper electrode. Current flows only if the two
halves of the cell are connected by a salt bridge. A salt bridge is often made from
filter paper soaked in a relatively unreactive electrolyte, such as a solution of
potassium nitrate.
These observations lead to the following explanations about what is occurring
in a galvanic cell.
• The reaction in the cell is a redox reaction, because electrons are being
transferred.
• The zinc electrode corrodes because the zinc metal forms zinc ions in solution:
Zn(s) → Zn2+(aq) + 2e–
• The oxidation of the zinc metal releases electrons, which flow through the wire
to the copper electrode.
• Electrons are accepted by copper(II) ions in the solution when the ions collide
with the copper electrode:
Cu2+(aq) + 2e– → Cu(s)
• The copper metal that is formed deposits on the electrode as a dark brown
coating.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 127


In this cell, there is a transformation of chemical energy to electrical energy.
Figure 5.1.5 shows the processes that occur during the operation of the cell.
The equation for the overall reaction is found by adding the two half-equations:
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)

salt bridge

zinc copper
e– e–

e– e–

NO3– K+
Zn
Cu2+
Cu
Zn2+
Zn
Cu2+
Zn
Cu2+

Zn(s) → Zn2+(aq) + 2e– Cu2+(aq) + 2e– → Cu(s)

FIGURE 5.1.5

This redox reaction is described as a spontaneous reaction because it occurs


naturally.
Copper(II) ions act as the oxidising agent, or oxidant, and zinc metal acts as
the reducing agent, or reductant.

A chemical that causes another substance to be oxidised is called an oxidising


agent and is itself reduced in the redox reaction. Similarly, a chemical that
causes another substance to be reduced is called a reducing agent. Reducing
agents are oxidised in redox reactions.

ENERGY TRANSFORMATIONS IN DIRECT REACTIONS


You may have seen a similar reaction to the one that occurs in a Daniell cell if
you have copper-plated a piece of metal, such as zinc. When zinc is immersed in
an aqueous solution containing Cu2+(aq) ions, the metal becomes coated in dark
brown copper (Figure 5.1.6). At the same time, thermal energy is produced, which
escapes into the surrounding environment as heat.
FIGURE 5.1.6 Cu2+ The overall equation for this metal displacement reaction is:
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)

128 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
This reaction is an example of a spontaneous exothermic reaction. If the galvanic electrical
reactants are allowed to come into direct contact with each other, their chemical cell energy
energy is transformed directly to thermal energy. However, in a galvanic cell, the chemical
energy
half-reactions occur in separate containers, and the electrons are transferred by the
direct heat
external circuit so that chemical energy is transformed into electrical energy. reaction energy
The energy changes that occur in galvanic cells and when reactants undergo
direct reaction are summarised in Figure 5.1.7. FIGURE 5.1.7

HOW A GALVANIC CELL OPERATES


A galvanic cell is designed so that half-reactions occur in two separate compartments
of the cell. Because the oxidising agent and reducing agent do not come into direct
contact with each other, electrons can only be transferred through an external
circuit connecting the negative and positive electrodes.
This flow of electrons creates an electric current. Therefore, the chemical energy
of the reactants is transformed into electrical energy.

Half-cells
A galvanic cell can be regarded as consisting of two half-cells. Each half-cell
contains an electrode in contact with a solution (see Figure 5.1.8). In the Daniell
cell, one half-cell contains Cu(s) and Cu2+(aq); the other contains Zn(s) and
Zn2+(aq). The species present in each half-cell forms a conjugate redox pair (an
oxidising agent and its corresponding reduced form).
If one member of the conjugate pair in a half-cell is a metal, it is usually used as
the electrode. Some redox pairs, such as Br2(aq)/Br–(aq) and Fe3+(aq)/Fe2+(aq), do
not involve solid metals. If no metal is present, an inert (unreactive) electrode, such
as platinum or graphite, is used, as shown in Figure 5.1.8.
silver platinum
electrode electrode

Ag+(aq)
Fe3+(aq) and
Fe2+(aq)

Ag+(aq)/Ag(s) half-cell Fe3+(aq)/Fe2+(aq) half-cell


3+ 2+ platinum electrode
FIGURE 5.1.8

H2(g) glass tube

In some half-cells, one of the conjugate pairs may be a gas. In such cases, the
special ‘gas electrode’ like the one shown in Figure 5.1.9 for the H+(aq)/H2(g) half- H+(aq)
cell is used. Note that half-cells usually contain other species not involved in the
reaction, such as spectator ions and the solvent.
The electrode at which oxidation occurs is called the anode. In a galvanic cell,
the anode, where electrons are released, is described as the negative terminal. The
electrode at which reduction occurs is called the cathode. The cathode, where
electrons are gained, is the positive terminal in a galvanic cell. H+(aq)/H2(g) half-cell

The purpose of the salt bridge FIGURE 5.1.9 A H+ 2


+
2
The salt bridge contains ions that are free to move so that they can balance charges
formed in the two compartments. Cations move towards the cathode and anions
move towards the anode.
Without a salt bridge, the solution in one compartment in the galvanic cell Cations in the salt bridge move
would accumulate negative charge and the solution in the other compartment towards the cathode and anions
would accumulate positive charge as the reaction proceeded. Such accumulation of in the salt bridge move towards
charge would stop the reaction very quickly and, hence, prevent further reaction.
The salt bridge is also called the internal circuit.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 129


WRITING HALF-CELL EQUATIONS
If a conjugate redox pair consists of an element and its corresponding ion, then
the half-equation is relatively easy to write. For instance, knowing that a reduction
reaction involves the conjugate redox pair of Zn2+ ions and Zn, you can quickly
write the half-cell equation as:
Zn2+(aq) + 2e– → Zn(s)
Half-cell equations involving polyatomic ions may be more complex to write.
The equation for the reduction reaction in a half-cell containing the dichromate ion
(Cr2O72–) and Cr3+ ion redox pair is:
Cr2O72–(aq) + 14H+(aq) + 6e– → 2Cr3+(aq) + 7H2O(l)
You learned to write half-equations such as these in Chapter 4.

Writing an overall equation for a cell reaction


The half-equations for the oxidation and reduction reactions that occur in a cell can
be added together to obtain an overall, or full, equation. An overall equation does
not show any electrons; all the electrons lost in the oxidation reaction are gained in
the reduction reaction. You may need to multiply one or both half-equations by a
factor to ensure that the electrons balance and can be cancelled out in the overall
equation.

The number of electrons lost in the oxidation reaction must equal the number

DRAWING AND LABELLING A DIAGRAM OF A GALVANIC


CELL
If you know the reaction occurring in a galvanic cell, then you can draw a diagram
of the cell identifying key features, such as the anode, cathode, electrode polarity,
direction of electron flow and direction of the flow of ions.
For example, consider a cell with the cell reaction:
Cu(s) + Cl2(g) → Cu2+(aq) + 2Cl–(aq)
From this reaction, you can see that:
• copper metal is at the anode (because copper is oxidised and oxidation occurs
at the anode)
• chlorine gas is present at the cathode (because chlorine is reduced and reduction
occurs at the cathode).
As in all galvanic cells:
• electrons flow through the external circuit from the anode (negative) to the
cathode (positive)
• anions flow in the internal circuit to the anode and cations flow towards
the cathode.

130 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
This information is used to draw and label the diagram of the cell as shown in
Figure 5.1.10.

galvanometer

+
_
chlorine gas

platinum cathode
copper anode

cations anions

Cl‒ solution Cu2+ solution

Cl2(g) + 2e‒ → 2Cl‒(aq) Cu(s) → Cu2+(aq) + 2e–


– 2+
FIGURE 5.1.10 2

5.1 Review
SUMMARY

• The reactions that occur in galvanic cells are • These key concepts about a galvanic cell are
spontaneous and exothermic. summarised in Figure 5.1.11.
• In a galvanic cell, chemical energy is converted
directly into electrical energy in a redox reaction.
galvanometer
• A cell is made from two half-cells.
ow
• Each half-cell contains a conjugate redox pair. on
tr

• An oxidation reaction occurs in one half-cell and


elec

a reduction reaction occurs in the other half-cell.


anode cathode
• The electrode in the half-cell in which oxidation
– +
occurs is called the anode; the electrode in the half-
cell in which reduction occurs is called the cathode. salt bridge
• In galvanic cells, the anode is negative and the
cathode is positive.
• Electrons flow through the external circuit from the
anode to the cathode. anions cations

• A salt bridge allows a cell to produce electricity by


preventing the accumulation of charge. Cations
oxidation at anode reduction at cathode
in the salt bridge move towards the cathode and
anions move towards the anode. FIGURE 5.1.11

• If the reactants in a galvanic cell reaction are


allowed to come into direct contact, chemical energy
is converted into heat energy rather than electrical
energy.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 131


KEY QUESTIONS

1 Which one of the following statements about a galvanic cell is correct?


A The electrode where oxidation occurs is the cathode.
B Electrons flow towards the electrode where oxidation occurs.
C Anions flow into the half-cell containing the electrode where reduction
occurs.
D The electrode where oxidation occurs has a positive polarity.
2 Draw labelled diagrams of the following half-cells.
a Ni2+(aq)/Ni(s)
b Sn4+(aq)/Sn2+(aq)
c H+(aq)/H2(g)
3 The overall equation for the reaction that occurs in a cell made up of
Al3+(aq)/Al(s) and Sn2+(aq)/Sn(s) half-cells is:
2Al(s) + 3Sn2+(aq) → 2Al3+(aq) + 3Sn(s)
Write half-equations for the reaction occurring at the:
a cathode
b anode.
4 Draw a diagram of the cell from Question 3 and label the:
• half-equation for the reaction occurring in each half-cell
• anode and cathode
• direction of electron flow
• electrode polarities (which electrode is positive and which is negative)
• direction of anion and cation flow from the salt bridge.
5 In the spaces provided, label the galvanic cell in Figure 5.1.12 with:
• anode
• cathode
• positive electrode
• negative electrode
• reduction
• oxidation
• salt bridge.

Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq)

Cu2+(aq) + 2e– Cu(s) Zn(s) Zn2+(aq) + 2e–

FIGURE 5.1.12

132 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
5.2 The electrochemical series
As you saw in Chapter 4, metals vary in their reactivity. Platinum and gold are
unreactive and widely used for jewellery. Other metals are very reactive. For
example, sodium reacts so readily with oxygen and water (Figure 5.2.1) that it
must be stored in paraffin oil.
Galvanic cells can help you compare the relative reactivity of metals. Galvanic
cells can be constructed from various combinations of half-cells. The experimental
data collected from these combinations allows chemists to determine the oxidising
and reducing strengths of many different substances. This information is very
useful, because it allows you to predict the products of various reactions, calculate
the voltages of cells and develop more powerful and longer-lasting batteries.

RELATIVE OXIDISING AND REDUCING STRENGTHS


A half-cell contains a conjugate redox pair. The reactions that can occur in a half-
cell can be written as reversible reactions, showing the relationship between the two FIGURE 5.2.1
chemicals in the redox pair. For example, the reaction in a:
• half-cell containing the H+(aq)/H2(g) redox pair may be written as:
2H+(aq) + 2e– H2(g)
• half-cell containing the Zn2+(aq)/Zn(s) redox pair may be written as:
Zn2+(aq) + 2e– Zn(s)
Figure 5.2.2 shows a diagram of a cell constructed from H+(aq)/H2(g) and
2+
Zn (aq)/Zn(s) half-cells.
galvanometer

+
_
hydrogen gas

platinum cathode
zinc anode

2H+(aq) + 2e‒ → H2(g) H+ solution Zn2+ solution Zn(s) → Zn2++ 2e‒


+ 2+
FIGURE 5.2.2 2

Notice that in this cell the zinc electrode is negative. The reactions that are
occurring are:
2H+(aq) + 2e– → H2(g)
Zn(s) → Zn2+(aq) + 2e–
2+ +
Zn is oxidised to Zn and H is reduced to H2. Zinc can be described as a
reducing agent or reductant because it causes the reduction of H+ to occur. The H+
is described as an oxidising agent or oxidant because it causes the Zn to be oxidised In a galvanic cell, the stronger
to Zn2+. reducing agent is in the half-
cell with the negative electrode
Because electrons flow from the Zn2+/Zn half-cell to the H+/H2 half-cell, we can
(anode). The stronger oxidising
infer that:
agent is in the half-cell with the
• zinc is a stronger reducing agent than H2 positive electrode (cathode).
• H+ is a stronger oxidising agent than Zn2+ ions.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 133


POTENTIAL DIFFERENCE
A current flows in a galvanic cell because one half-cell has a greater tendency to
push electrons into the external circuit than the other half-cell. Chemists say that a
potential difference exists between the two half-cells. The potential difference of
a cell is sometimes also called the electromotive force, or emf, and is commonly
referred to as the voltage.
The potential difference of a cell, symbol E, has the unit of a volt (V) and is
measured with a voltmeter.
Potential differences of cells are usually measured under the standard
conditions of:
• a pressure of 1 bar (100 kPa)
• 1 M concentration of solutions.
The potential difference of a cell under standard conditions is given the
symbol E°. Potential differences are usually measured at 25°C.

Standard electrode potentials


It is impossible to measure the potential difference of an isolated half-cell because
both oxidation and reduction must take place for a potential difference to exist.
However, you can assign a standard half-cell potential (E°) to each half-cell by
connecting the cells to a standard reference half-cell and measuring the voltage
produced.
A hydrogen half-cell, H+(aq)/H2(g), under standard conditions, is used for this
purpose and its E° value is arbitrarily assigned as zero. This half-cell is known as the
standard hydrogen half-cell or standard hydrogen electrode.
The standard electrode potential of other cells may then be measured by
connecting them to the standard hydrogen half-cell, as shown in Figure 5.2.3 for
the Fe2+(aq)/Fe(s) half-cell.
voltmeter

electron

0.44 V
+
H2(g)

platinum electrode
iron electrode

H+(aq) Fe2+(aq)
Both cells are under standard conditions.
2+
FIGURE 5.2.3

We can summarise the information obtained from this measurement shown in


Figure 5.2.3 as follows:
Fe2+(aq) + 2e– Fe(s) E° = –0.44 V
The negative sign indicates that the electrode in the half-cell was negative when
connected to the hydrogen half-cell. Oxidation is occurring in the Fe2+(aq)/Fe(s)
half-cell and the electrons that are produced from the iron electrode move towards
the hydrogen half-cell. The value of –0.44 V is known as both the standard electrode
potential and the standard reduction potential. The standard electrode potential
gives a numerical measure of the tendency of a half-cell reaction to occur as a
reduction reaction.
134 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
THE ELECTROCHEMICAL SERIES
By connecting the standard hydrogen electrode to different half-cells and measuring
their standard reduction potentials, chemists have developed a table called the
electrochemical series (Table 5.2.1).

TABLE 5.2.1

Oxidising agents Reducing agents E° (V)


– –
F2(g) + 2e 2F (aq) +2.87
+ –
H2O2(aq) + 2H (aq) + 2e 2H2O(l) +1.77
+ –
Au (aq) + e Au(s) +1.68

Cl2(g) + 2e– 2Cl–(aq) +1.36

O2(g) + 4H+(aq) + 4e– 2H2O(l) +1.23

Br2(l) + 2e– 2Br–(aq) +1.09

Ag+(aq) + e– Ag(s) +0.80

Fe3+(aq) + e– Fe2+(aq) +0.77

O2(g) + 2H+(aq) + 2e– H2O2(aq) +0.68


– –
I2(s) + 2e 2I (aq) +0.54
– –
O2(g) + 2H2O(l) + 4e 4OH (aq) +0.40
Increasing oxidising strength

Increasing reducing strength

2+ –
Cu (aq) + 2e Cu(s) +0.34
4+ – 2+
Sn (aq) + 2e Sn (aq) +0.15
+ –
S(s) + 2H (aq) + 2e H2S(g) +0.14
+ –
2H (aq) + 2e H2(g) 0.00
2+ –
Pb (aq) + 2e Pb(s) –0.13
2+ –
Sn (aq) + 2e Sn(s) –0.14
2+ –
Ni (aq) + 2e Ni(s) –0.23

Co2+(aq) + 2e– Co(s) –0.28

Fe2+(aq) + 2e– Fe(s) –0.44

Zn2+(aq) + 2e– Zn(s) –0.76

2H2O(l) + 2e– H2(g) + 2OH–(aq) –0.83

Mn2+(aq) + 2e– Mn(s) –1.03

Al3+(aq) + 3e– Al(s) –1.67


2+ –
Mg (aq) + 2e Mg(s) –2.34
+ –
Na (aq) + e Na(s) –2.71
2+ –
Ca (aq) + 2e Ca(s) –2.87
+ –
K (aq) + e K(s) –2.93
Strong reducing agents donate
+ –
Li (aq) + e Li(s) –3.02 electrons more readily than

Under non-standard conditions, the order of the half-cells may change. Strong oxidising agents accept
Notice the value of 0.00 V given for the H+(aq)/H2(g) half-equation. All other electrons more readily than
E° values are relative to this arbitrary standard. The strongest oxidising agent, F2,
is at the top left of the table and the strongest reducing agent, Li, is at the bottom Strong reducing agents have weak
right of the table. conjugate oxidising agents.
In a galvanic cell, the stronger reducing agent is oxidised so it is in the half-cell Strong oxidising agents have weak
with the negative electrode (anode). The stronger oxidising agent is reduced so it is conjugate reducing agents.
in the half-cell with the positive electrode (cathode).

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 135


USING THE ELECTROCHEMICAL SERIES
Predicting cell reactions
You can use the electrochemical series to predict what will happen when two specific
half-cells are combined to form a cell. The strongest oxidising agent in the cell will
react with the strongest reducing agent.
Another way to predict the electrode reactions is to remember that the half-
reaction that is higher in the electrochemical series goes forward and the lower one
is reversed. As a consequence:
• a reduction reaction will occur in the half-cell with the higher E° value, whereas
an oxidation reaction will occur in the half-cell with the lower E° value
• the positive electrode will be in the half-cell with the higher E° value, whereas the
negative electrode will be in the other half-cell.
The equation for the overall cell reaction is found by adding the two half-
equations. Worked Example 5.2.1 shows you how to use the electrochemical series
to predict a cell reaction.

Worked example 5.2.1


PREDICTING THE OPERATION OF A GALVANIC CELL

A cell is made from Ag+(aq)/Ag(s) and Fe2+(aq)/Fe(s) half-cells under standard


conditions and 25°C. Use the electrochemical series to predict the overall
cell reaction, identify the anode and cathode, and determine the direction of
electron flow.

Thinking Working

Identify the two relevant half- Ag+(aq) + e– Ag(s) E° = 0.80 V


equations in the electrochemical Fe2+(aq) + 2e– Fe(s) E° = –0.44 V
series.

Identify the strongest oxidising Because Ag+ is higher on the left side of the
agent (the species on the left of table than Fe2+, it is the stronger oxidising
the series with the most positive agent.
E° value) and the strongest Fe, being lower on the right side of the table
reducing agent (bottom right). than Ag, is a stronger reducing agent.

Write the two half-equations Reduction:


that will occur. The strongest Ag+(aq) + e– → Ag(s)
oxidising agent will react with
Oxidation:
the strongest reducing agent.
Fe(s) → Fe2+(aq) + 2e–
(Hint: The reduction equation
has the most positive E° value Because this is the oxidation reaction,
and the oxidation equation has the equation should be written in reverse.
the most negative E° value.)

Write the overall cell equation. Multiply the Ag+/Ag half-cell equation by
two so that the number of electrons in each
half-equation is equal, and then add the two
equations together:
[Ag+(aq) + e– → Ag(s)] × 2
Fe(s) → Fe2+(aq) + 2e–
2Ag+(aq) + Fe(s) → 2Ag(s) + Fe2+(aq)

Identify the anode and the The silver electrode will be the cathode
cathode in this cell. The anode is and the iron electrode will be the anode.
the electrode at which oxidation
occurs. The cathode is the
electrode at which reduction
occurs.

136 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Determine the polarities of the Electrons flow from the negative electrode (anode) to the positive
electrodes and the direction of electrode (cathode) as shown in Figure 5.2.4.
electron flow in the cell.
The anode is negative;
voltmeter
the cathode is positive.

– +

iron silver
anode cathode

Fe2+(aq) Ag+(aq)

2+ +
FIGURE 5.2.4

Worked example: Try yourself 5.2.1


PREDICTING THE OPERATION OF A GALVANIC CELL

A cell is made from Sn2+(aq)/Sn(s) and Ni2+(aq)/Ni(s) half-cells under standard


conditions and at 25°C. Use the electrochemical series to predict the overall
cell reaction, identify the anode and cathode, and determine the direction of
electron flow.

The maximum potential difference of a cell under standard conditions is the


difference between the E° values of its two half-cells. It is defined as follows:
cell potential E° of half-cell containing E° of half-cell containing
= –
difference the oxidising agent the reducing agent
An easy way to remember this for galvanic cells is:
cell potential difference = higher half-cell E° – lower half-cell E°
For example, the maximum cell voltage of a cell constructed from Ag+(aq)/
Ag(s) and Fe2+(aq)/Fe(s) half-cells under standard conditions can be calculated
as follows:
cell potential difference = higher half-cell E° – lower half-cell E°
= E°(Ag+(aq)/Ag(s)) – E°(Fe2+(aq)/Fe(s))
= 0.80 – (–0.44)
= 1.24 V
Different values for the cell voltage are obtained under non-standard conditions.
As a galvanic cell discharges, the cell voltage eventually drops to zero and the
cell is referred to as ‘flat’. Equilibrium has then been reached.

cell potential difference = higher half-cell E° – lower half-cell E°

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 137


5.2 Review
SUMMARY

• The standard hydrogen half-cell is used as the • The relative strengths of oxidising and reducing
standard reference half-cell; its value is arbitrarily agents can be determined by comparing standard
assigned as zero. electrode potentials, and these can be used to
• The standard electrode potential or standard predict half-cell and overall cell reactions.
reduction potential (E°) of a half-cell is measured by • The maximum potential difference of a cell under
connecting the half-cell to a standard hydrogen half- standard conditions can be calculated from
cell and measuring the voltage produced. standard electrode potentials:
• The standard electrode potential gives a numerical E° of half-cell E° of half-cell
cell potential
measure of the tendency of a half-cell reaction to = containing the – containing the
difference
occur as a reduction reaction. oxidising agent reducing agent
• Standard electrode potentials are used as the basis A simple way of remembering this is:
of the electrochemical series. cell potential
= higher half-cell E° – lower half-cell E°
• In the electrochemical series, half-reactions are difference
listed in order so that the strongest oxidising agent • For a spontaneous reaction to occur, an oxidising
is at the top left of the series (with the most positive agent (on the left of the electrochemical series) must
E° value) and the strongest reducing agent is at the react with a reducing agent (on the right) that is
bottom right (with the most negative E° value). lower in the series.
• The electrochemical series is valid for standard
conditions; that is, gas pressures of 1 bar and
solution concentrations of 1 M. Standard electrode
potentials are usually measured at 25°C.

KEY QUESTIONS

1 A galvanic cell was constructed from Al3+(aq)/Al(s) and Pb2+(aq)/Pb(s)


half-cells. Use the electrochemical series to predict the:
a oxidation and reduction half-equations
b overall cell reaction
c identity of the anode and cathode.
2 Draw a labelled diagram of a cell formed from Cl2(g)/Cl–(aq) and
Sn2+(aq)/Sn(s) half-cells. Use the electrochemical series to indicate the:
a half-cell reactions
b anode and cathode
c direction of electron flow
d electrode polarities (which electrode is positive and which is negative)
e directions of flow of the anions and cations in the salt bridge
f overall reaction.
3 Repeat Question 2 for the cells formed from the following half-cells.
a Fe3+(aq)/Fe2+(aq) and H+(aq)/H2(g)
b Cl2(g)/Cl–(aq) and Pb2+(aq)/Pb(s)
4 Calculate the cell potential difference for each of the cells in Questions 1–3.

138 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
5.3 Predicting direct redox reactions
The electrochemical series provides us with a ranking of the relative strengths of
oxidising and reducing agents.
In this section, you will see that you can apply your understanding of the Oxidising Reducing
electrochemical series to predict the likelihood of a redox reaction taking place agents agents
when different chemicals are combined. A2+ is reduced to A
A2+ A
reac
ts w
PREDICTING REACTIONS ith
If the contents of the half-cells of a galvanic cell were mixed, the reactants would B is oxidised to B2+
react directly. Energy would be released as heat rather than as electrical energy. B2+ B
Reactions that occur in galvanic cells or when chemicals are directly mixed are A2+ reacts with B.
described as naturally occurring reactions, or spontaneous reactions. No reaction occurs for the other
In the last section, you saw that in a galvanic cell the strongest oxidising agent combinations: A and B, A2+ and B2+,
in the cell reacts with the strongest reducing agent. In other words, the higher half- A2+ and A, A and A2+, A2+ and B.
reaction (the one with the most positive E° value) in the electrochemical series FIGURE 5.3.1
occurs in the forward direction (as reduction) and the lower reaction (the one with
the most negative E° value) occurs in the reverse direction (as oxidation).
This principle applies equally to redox reactions that occur when reactants are
mixed directly.
As shown in Figure 5.3.1, for a spontaneous reaction to occur, an oxidising With half-equations arranged in
agent (on the left of the electrochemical series) must react with a reducing agent order of increasing reducing agent
(on the right) that is lower in the electrochemical series. strength, you can predict that a
spontaneous reaction will occur
Worked example 5.3.1 by looking for substances that are
arranged in a top-left/bottom-right
PREDICTING DIRECT REDOX REACTIONS
position.
Consider the following equations that appear in the order shown in the
electrochemical series.
Br2(aq) + 2e– 2Br –(aq) E° = +1.09 V
2+ –
Ni (aq) + 2e Ni(s) E° = –0.23 V
Mg2+(aq) + 2e– Mg(s) E° = –2.34 V

Use the electrochemical series to predict the effect of mixing:


a Br2(aq) and Mg2+(aq) b Mg2+(aq) and Ni(s) c Ni2+(aq) and Mg(s).

Thinking Working

Identify the two relevant a Br2(aq) + 2e– 2Br–(aq) E° = +1.09 V


half-equations in the 2+
Mg (aq) + 2e –
Mg(s) E° = –2.34 V
electrochemical series.
No reaction occurs because both Br2(aq) and Mg2+(aq) are oxidising agents.
Predict whether
b Ni2+(aq) + 2e– Ni(s) E° = –0.23 V
or not a reaction
occurs. A chemical Mg2+(aq) + 2e– Mg(s) E° = –2.34 V
species on the left (an No reaction occurs because the oxidising agent, Mg2+, is below the reducing
oxidising agent) of the agent, Ni, in the electrochemical series.
electrochemical series c Ni2+(aq) + 2e– Ni(s) E° = –0.23 V
reacts with a chemical
Mg2+(aq) + 2e– Mg(s) E° = –2.34 V
species on the right (a
reducing agent) that is A reaction occurs because the oxidising agent, Ni2+, is above the reducing
lower in the series. agent, Mg, in the electrochemical series.
Write the overall The higher half-equation occurs in the forward direction:
equation. Ni2+(aq) + 2e– → Ni(s)
The lower half-equation occurs in the reverse direction:
Mg(s) → Mg2+(aq) + 2e–
The overall reaction equation is found by adding the half-equations:
Ni2+(aq) + Mg(s) → Ni(s) + Mg2+(aq)

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 139


Worked example: Try yourself 5.3.1
PREDICTING DIRECT REDOX REACTIONS
Consider the following equations that appear in the order shown in the
electrochemical series:
Cl2(g) + 2e– 2Cl–(aq) E° = +1.36 V

I2(s) + 2e 2I–(aq) E° = +0.54 V
2+ –
Pb (aq) + 2e Pb(s) E° = –0.13 V

Use the electrochemical series to predict the effect of mixing:


a I2(s) and Pb2+(aq)
b Cl–(aq) and I2(s)
c Cl–(aq) and Pb(s).

CHEMFILE
The thermite reaction
The thermite reaction is a highly exothermic reaction between powdered aluminium
and iron(III) oxide.

Fe3+ + 3e– Fe E° = –0.036 V


Al3+ + 3e– Al E° = –1.67 V
A spontaneous reaction is predicted to occur because the oxidising agent, Fe3+, is

The thermite reaction releases so much heat that it is enough to melt the iron that
is produced. One use for the thermite reaction is for welding together railway tracks
(Figure 5.3.2).

FIGURE 5.3.2

LIMITATIONS OF PREDICTIONS
The standard half-cell potentials given in the electrochemical series are measured
under standard conditions. As you would expect, half-cell potentials can vary under
other conditions.
When conditions are very different from standard conditions, the order of half-
reactions in the electrochemical series may also be different, and predictions of
reactions based on the standard half-cell potentials may not be reliable.
It is also important to remember that the electrochemical series gives no
information about the rate at which reactions occur.

140 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
5.3 Review
SUMMARY

• The relative strength of oxidising and reducing • When reactants react in a galvanic cell, chemical
agents can be determined by comparing standard energy is transformed into electrical energy.
electrode potentials, and these can be used to However, when they react directly, their chemical
predict the tendency of a reaction to occur, both energy is transformed into heat energy.
in galvanic cells and in direct reactions. • The standard half-cell potentials in the
• For a spontaneous reaction to occur, an oxidising electrochemical series are measured under standard
agent (on the left of the electrochemical series) must conditions. Under other conditions, the order of half-
react with a reducing agent (on the right) that is reactions may be different, and predictions based
lower in the series. on the electrochemical series may not be reliable.
• Overall equations for redox reactions can be
obtained by adding half-equations.

KEY QUESTIONS

1 Which one of the following metals would you expect to be coated with lead
when immersed in a solution of lead(II) nitrate?
A Copper
B Cobalt
C Silver
D Gold
2 Which one of the following species would react with H2S(g) but not with
H2O(l) under standard conditions?
A Cl2(g)
B Mg(s)
C Ag+(aq)
D Cu(s)
3 Using the electrochemical series, predict whether a reaction will occur in the
following situations. If a reaction does occur, write the overall equation for
the reaction.
a Chlorine gas is bubbled into a solution containing bromide ions.
b Chlorine gas is bubbled into a solution containing iodide ions.
c A bromine solution is added to a solution containing chloride ions.
d A bromine solution is added to a solution containing iodide ions.
4 A reaction occurs when a strip of zinc metal is placed in a silver nitrate
solution.
a Write the overall equation for the reaction.
b Describe the energy change that takes place in this reaction.
5 Iron nails are placed into 1 M solutions of CuSO4, MgCl2, Pb(NO3)2 and
ZnCl2. Use the electrochemical series to identify in which solution(s) you
would expect a coating of a metal other than iron to appear on the nail.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 141


5.4 Everyday sources of power
The battery was invented by Alessandro Volta in 1800. More than two centuries
later, cells and batteries are a common power source for many household and
industrial applications. Cells and batteries can be used as fixed energy storage
systems, such as in solar energy systems, burglar alarms and smoke detectors.
They are also used extensively in portable applications, including mobile phones,
watches, digital cameras and laptop computers. The portability of these devices
relies on these sources of electrical energy.
Cells and batteries use spontaneous redox reactions as the source of energy. In
this section, you will look at the two main types of cells in use and how chemical
reactions in these cells are used to produce electricity for everyday applications.
The two basic types of cells are:
• primary cells, which are disposable and designed not to be recharged
• secondary cells, which are rechargeable and designed to be reused many
times.
Both primary cells and secondary cells are types of galvanic cells.

PRIMARY CELLS
Common commercial alkaline cells, such as those you would usually use in a
torch or a remote control, are non-rechargeable cells (Figure 5.4.1). They ‘go
FIGURE 5.4.1 flat’ when the cell reaction reaches equilibrium, and you have to buy a replacement.
Cells that cannot be recharged are called primary cells. In primary cells, the
products slowly migrate away from the electrodes or are consumed by side reactions
occurring in the cell, preventing the cells from being recharged.

EXTENSION
metal cap (+)
Primary cells—alkaline cells cathode:
outer steel
case
Following World War II, an expanding range of electrical
appliances became available that required small, high- powdered
capacity power sources. With earlier types of cells unable zinc
to meet these demands, the alkaline cell was developed in
mixture of
the late 1960s. manganese dioxide
Figure 5.4.2 shows the construction of an alkaline cell. and carbon
This cell is similar to the simple galvanic cells looked at
potassium hydroxide
earlier in this chapter, but has been designed so the two
electrolyte
half-reactions occur in separate places within the one
container. A potassium hydroxide electrolyte performs the anode: steel
or brass
same function as a salt bridge in the simple cells.
An alkaline cell needs less electrolyte than a dry cell,
metal base (–)
which it has largely replaced for household use. The
smaller quantity of electrolyte allows more reactant to be FIGURE 5.4.2
included. A typical D size alkaline cell contains about 40 g
of manganese dioxide, compared with 25 g in a dry cell of • At the cathode (+), manganese dioxide is reduced:
equivalent size.
2MnO2(s) + H2O(l) + 2e– → Mn2O3(s) + 2OH–(aq)
The following reactions occur in an alkaline cell.
Alkaline cells are especially cost-effective in torches,
• At the anode (–), zinc powder around the central metal flashguns and motorised toys, where high currents are
rod is oxidised and reacts with hydroxide ions, forming needed intermittently. The cell produces about 1.5 V.
zinc hydroxide: Once the reaction in the cell reaches equilibrium, the cell
Zn(s) + 2OH–(aq) → Zn(OH)2(s) + 2e– is ‘flat’, and cannot be used again.

142 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHEMFILE
Powering the Overland Telegraph

Leclanché cell. It had a similar overall cell reaction to the reaction in alkaline cells.
Leclanché cells were one of the sources of power for the Australian Overland Telegraph

telegraph line was completed in 1872 and connected Darwin in the Northern Territory
with Port Augusta in South Australia, allowing fast communication between Australia and

FIGURE 5.4.3

RECHARGEABLE CELLS AND BATTERIES


Rechargeable cells such as lithium-ion cells and nickel–metal hydride cells,
are known as secondary cells or accumulators.
Rechargeable cells and batteries have become very popular and are found in
mobile phones, laptop computers, cameras and portable power tools. They are also
fundamental to the operation of electric vehicles and solar power energy storage
systems.
Most types of rechargeable cells can undergo many hundreds of recharges. To
recharge a cell, the cell reaction must occur in reverse: the products of the reaction
must be converted back into the original reactants. This is done by connecting the
cell to a ‘charger’, a source of electrical energy, which has a potential difference a
little greater than the potential difference of the cell. The positive terminal of the
charger is connected to the cell’s positive electrode and the negative electrode of the
charger to the cell’s negative electrode (see Figure 5.4.4).
Electrical energy supplied by the charger is converted into chemical energy FIGURE 5.4.4
in the cell. In order for it to be possible to regenerate the reactants, the products
formed in the cell during discharge must remain in contact with the electrodes in a
convertible form.
The energy transformations in a secondary cell can be summarised as follows.
• When a secondary cell discharges, it acts as a galvanic cell, converting chemical
energy into electrical energy.
• When the cell is recharged, it acts as a type of cell called an electrolytic cell.
Electrical energy is transformed into chemical energy in an electrolytic cell.
You will learn more about the operation of electrolytic cells in Chapter 9.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 143


Discharging During the discharging process in a secondary cell:
• oxidation occurs at the negative terminal (the anode)
• reduction occurs at the positive terminal (the cathode).
However, when the cell is recharging, the cell reaction is reversed:
• oxidation occurs at the positive terminal (the anode)
electrical • reduction occurs at the negative terminal (the cathode).
energy energy
The energy transformations and redox processes that occur during the
discharging and recharging of a secondary cell are summarised in Figure 5.4.5.
Recharging
When a secondary cell is recharged, the reactions are reversed at each

FIGURE 5.4.5

EXTENSION

Secondary batteries—car batteries


Lead–acid batteries are the most widely used type of
secondary cell. They are relatively cheap and reliable,
provide high currents, and have a long lifetime.
Most people know the lead–acid battery simply as a car
battery (Figure 5.4.6). It is used to start the car’s engine
and to operate the car’s electrical accessories when the
engine is not running. Once the engine starts, an alternator,
which is run by the engine, provides electrical energy
to operate the car’s electrical system and recharge
the battery.

porous
separator sulfuric acid

lead plates lead plates (‒)


impregnated with
lead(IV) oxide (+)
FIGURE 5.4.6
FIGURE 5.4.7

Each cell has a potential difference of just over 2 V. A car


Lead–acid batteries are also used for emergency light
battery has six of these cells connected in series, giving a
and power systems, for small-scale energy storage and
total potential difference of about 12 V.
to power some electric vehicles such as golf buggies and
small fork lifts. The following reactions occur in a lead–acid battery as
it produces electricity.
As shown in the diagram in Figure 5.4.7, a modern
lead–acid battery is actually six separate cells connected • At the anodes (–), lead is oxidised to Pb2+ ions:
together in series. The positive electrodes consist of a Pb(s) + SO42–(aq) → PbSO4(s) + 2e–
lead grid packed with lead(IV) oxide (PbO2) while the • At the cathodes (+), lead(IV) oxide is reduced to Pb2+
negative electrodes consist of a lead grid packed with ions:
powdered lead. A solution of sulfuric acid, of about 4 M PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– →
concentration, acts as the electrolyte. PbSO4(s) + 2H2O(l)

144 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
The two half-equations can be combined as an overall about 14 V, is used to force electrons into the battery’s
equation: negative terminal and draw them out at the positive
Pb(s) + PbO2(s) + 2SO42–(aq) + 4H+(aq) → terminal, in effect driving the spontaneous reaction
2PbSO4(s) + 2H2O(l) backwards. The recharging process converts electrical
The product of both electrode reactions, lead(II) sulfate, energy into chemical energy.
forms as a solid on the surface of the electrodes. This The overall equation for the reaction as the battery
enables the battery to be recharged. recharges is:
To recharge the battery, the electrode reactions are 2PbSO4(s) + 2H2O(l) →
reversed. The alternator, with a potential difference of Pb(s) + PbO2(s) + 2SO42–(aq) + 4H+(aq)

Battery life
The term battery life is used in several ways to describe the performance of a cell
or battery. You might use the term to simply describe the time the battery operates
in your phone following a full charge, but in technical specifications battery life
normally refers to the number of charge–discharge cycles before a battery becomes
unusable.
Batteries have a limited life because unwanted physical and chemical changes
occur within them. A battery’s performance deteriorates at each charge–discharge
cycle. Modern batteries have lifetimes of 500–1200 cycles, but may continue to be
useful for up to 2000 cycles, although the battery capacity (amount of charge
available) may drop to 80% of the original value.
Many factors influence how the performance of a battery decreases over time.
These include:
• loss of active materials (reactants and products of the cell reaction). Active
material may become detached from the electrode on each cycle or be slowly
converted into inactive forms by side reactions
• progressive conversion of small crystals of active material at the electrodes into
larger crystals at each cycle, which increases resistance to current flow
• formation of other chemicals in side reactions that impede the efficient
functioning of the cell
• impurities in cell materials, including the electrodes, which can react with active
materials
• decrease in contact of electrolyte with electrodes, either through leakage of
electrolyte or its transformation into a non-conductive material
• corrosion or failure of internal components.
The graph in Figure 5.4.8 (on page 146) summarises the effect of temperature
on both battery life and battery capacity.
The rate of deterioration of a battery depends on temperature: the higher the
temperature, the faster the deterioration occurs. Batteries release heat energy under
normal operation. As the battery operating temperature rises, the rate of the side
reactions increases and the battery life becomes shorter. Nickel–metal hydride
batteries are particularly sensitive to the effect of heat.
Conversely, because the rates of reactions fall as temperature decreases, batteries
can deliver less electric charge at a specific discharge rate under cold conditions
and battery capacity decreases. In summary, cold conditions are not good for the
performance of a battery; warmer conditions are not good for battery life.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 145


× operation not recommended
capacity battery life
200

180

160

Battery life and battery capacity (%)


140

120

100

80

60

40

20

0
×

×
–20 –10 0 10 15 20 25 30 35 40 50 60
Temperature (°C)

FIGURE 5.4.8

Side reactions and deterioration continue even when batteries are not in use,
in a process called self-discharge. The life of a battery that is not in use can be
extended by storing it at a low temperature in a refrigerator, which slows the side
reactions.

5.4 Review
SUMMARY

• Primary and secondary cells are examples of • For a secondary cell, the anode, where oxidation
galvanic cells. occurs, is the negative terminal during discharging
• Primary cells cannot be recharged. but the positive terminal during recharging.
• Secondary cells can be recharged by connecting • When a secondary cell discharges and produces
them to an external source of electricity. electrical energy, it acts as a galvanic cell; when it is
• For a cell to be rechargeable, the products of the recharged, it acts as an electrolytic cell.
discharge reaction have to remain in contact with • Battery life decreases over time, due in part to side
the electrodes. reactions that reduce the amount of active material
• During the recharging of a secondary cell, the in a battery.
cell reaction is reversed and the products of the • The rate of deterioration of a battery increases as
cell reaction are converted back into the original temperature increases.
reactants. Therefore, the equation for the reaction
that occurs during the recharging of a secondary
cell is the reverse of the equation for the cell
discharging.

146 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
KEY QUESTIONS

1 Describe the key difference between a primary cell and a secondary cell.
2 Which one of the following statements is correct about a secondary cell
as it recharges?
A Oxidation occurs at the cathode, which acts as the negative terminal.
B Oxidation occurs at the cathode, which acts as the positive terminal.
C Oxidation occurs at the anode, which acts as the negative terminal.
D Oxidation occurs at the anode, which acts as the positive terminal.
3 Most modern mobile phones contain lithium-ion cells. Select the correct
statement about the process that occurs when a phone battery is recharged.
A A non-spontaneous reaction occurs and the lithium-ion cell acts as an
electrolytic cell.
B A non-spontaneous reaction occurs and the lithium-ion cell acts as a
galvanic cell.
C A spontaneous reaction occurs and the lithium-ion cell acts as an
electrolytic cell.
D A spontaneous reaction occurs and the lithium-ion cell acts as a
galvanic cell.
4 Decide whether each of the following statements about cells and batteries
is true or false.
a The rate of deterioration of a battery decreases as temperature decreases.
b Primary cells cannot be recharged effectively because their reaction
products are not in contact with the electrodes.
c Batteries only deteriorate as they undergo charge–discharge cycles.
d Side reactions in a battery can decrease battery life.
e In a secondary cell, all of the reactants and products of the cell reaction
remain in contact with the electrodes throughout the cell’s life.
f The life of a modern battery is not affected by the recharging process.
5 In a silver–zinc button cell, the cell reaction is:
Zn(s) + Ag2O(s) + H2O(l) → Zn(OH)2(s) + 2Ag(s)
The zinc acts as the anode and the cell contains a potassium hydroxide
electrolyte. Write a half-equation for the reaction occurring at the:
a anode
b cathode.

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 147


Chapter review
KEY TERMS

accumulator electrolyte oxidant


active material electrolytic cell oxidising agent
alkaline cell electromotive force potential difference
anode external circuit primary cell standard conditions
battery galvanic cell rechargeable cell standard electrode
battery capacity galvanometer redox reaction potential
battery life half-cell reducing agent standard hydrogen half-cell
cathode internal circuit reductant standard reduction
conjugate redox pair lead–acid battery salt bridge potential
electrochemical cell lithium-ion cell secondary cell volt
electrochemical series nickel–metal hydride cell self-discharge voltaic cell
electrode non-rechargeable cell spontaneous reaction voltmeter

Galvanic cells in potassium nitrate solution. When the electrodes are


1 Which one of the following statements best describes connected by wires to a galvanometer, the magnesium
the role of the salt bridge in a galvanic cell? electrode is shown to be negatively charged.
A It allows positive charges to accumulate in one a Sketch the galvanic cell described. Label the
half-cell and negative charges to accumulate in positive and negative electrodes. Mark the direction
the other. of the electron flow.
B It provides a pathway for electrons to move b Write the half-equations for the reactions that occur
between the half-cells. in each half-cell and an equation for the overall
C It allows reactants from one half-cell to mix with reaction.
reactants from the other half-cell. c Label the anode and cathode.
D It allows movement of ions to balance charges d Indicate the direction in which ions in the salt
formed at the electrodes. bridge migrate.
2 Which one of the following materials would be least The electrochemical series
suitable for use as an electrode in a Cl2(g)/Cl–(aq) 6 Show that under standard conditions, according to the
half-cell? electrochemical series, the Daniell cell (Figure 5.1.4,
A Iron B Platinum page 127) should have a cell potential difference
C Graphite D Gold of 1.10 V.
3 Explain the difference between: 7 The two galvanic cells shown in Figure 5.5.1 were
a oxidising agent and reducing agent constructed under standard conditions.
b anode and cathode
Pt Pt
c conjugate redox pair and conjugate acid–base pair
d external circuit and internal circuit.
4 The overall reaction for a galvanic cell constructed
from the Cl2(g)/Cl–(aq) and Pb2+(aq)/Pb(s) half-cells is:
Cl2(g) + Pb(s) → 2Cl–(g) + Pb2+(aq) Sn2+ Fe2+
Draw a diagram of the galvanic cell and on your Sn4+ Fe3+
diagram show:
a the direction of electron flow in the external circuit Pt Pt
b a half-equation for the reaction at each electrode
c which electrode is the anode
d which electrode is positive
e which way cations flow in the salt bridge.
5 Two half-cells are set up. One contains a solution of Fe2+ Br2
magnesium nitrate with a strip of magnesium as the Fe3+ Br –
electrode. The other contains lead nitrate with a strip
of lead as the electrode. The solutions in the two half- FIGURE 5.5.1

cells are connected by a piece of filter paper soaked

148 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
On the basis of the electrode polarities, determine Predicting direct redox reactions
the order of reducing agent strength from strongest 11 The following equations appear in the order shown
to weakest. in the electrochemical series:
8 Consider the four galvanic cells made from half-cells Cl2(g) + 2e– 2Cl–(aq)
as listed below. Use the electrochemical series to rank Ag+(aq) + e– Ag(s)
the galvanic cells in order of the maximum voltage Zn2+(aq) + 2e– Zn(s)
they could generate under standard conditions. i Predict whether a redox reaction would occur in
• Fe2+(aq)/Fe(s) and Fe3+(aq)/Fe2+(aq) the following mixtures. Assume concentrations of
• Ni2+(aq)/Ni(s) and Fe2+(aq)/Fe(s) 1 M and gas pressures of 1 bar.
• Ni2+(aq)/Ni(s) and Br2(l)/Br–(aq) For mixtures where you predict a reaction will
• Ni2+(aq)/Ni(s) and Fe3+(aq)/Fe2+(aq) occur, write:
9 Each of these pairs of half-cells combines to form ii separate half-equations for the oxidation and
a galvanic cell. reduction reactions
i Ag+(aq)/Ag(s) and Zn2+(aq)/Zn(s) iii an overall equation.
ii Fe2+(aq)/Fe(s) and Pb2+(aq)/Pb(s) a Cl2(g) and Zn(s)
iii Ni2+(aq)/Ni(s) and Cu2+(aq)/Cu(s) b Ag+(aq) and Ag(s)
Draw a diagram of each galvanic cell and on your c Ag+(aq) and Zn(s)
diagrams show: d Zn2+(aq) and Cl–(aq)
a the direction of electron flow in the external circuit 12 Use the electrochemical series to predict whether a
b a half-equation for the reaction at each electrode reaction will occur in each of the following situations.
c an equation for the overall reaction in the Write an equation for each reaction that you predict
galvanic cell will occur.
d which electrode is the anode a Copper(II) sulfate solution is stored in an aluminium
e which electrode is positive container.
f which way negative ions flow in the salt bridge. b Sodium chloride solution is stored in a copper
10 Four half-cells A2+(aq)/A(s), B2+(aq)/B(s), C2+(aq)/C(s) container.
and D2+(aq)/D(s) are used to make the cells shown in c Silver nitrate solution is stored in a zinc container.
Figure 5.5.2. d An iron nail is placed in 1 M hydrochloric acid
solution.
– +
e A plumber uses hydrochloric acid to clean copper
A B pipes.
13 The following equations form part of the electrochemical
series. They are ranked in the order shown.
Ag+(aq) + e– Ag(s)
A2+ B2+
Pb2+(aq) + 2e– Pb(s)
– + Fe2+(aq) + 2e– Fe(s)
C A Zn2+(aq) + 2e– Zn(s)
Mg2+(aq) + 2e– Mg(s)
a Which species is the strongest oxidising agent and
which species is the weakest oxidising agent?
C2+ A2+ b Which species is the strongest reducing agent and
– + which species is the weakest reducing agent?
D C c Lead rods are placed in solutions of silver nitrate,
iron(lI) sulfate and magnesium chloride. In which
solutions would you expect to see a coating of
another metal form on the lead rod? Explain.
D2+ C2+ d Which of the metals silver, zinc or magnesium
might be coated with lead when immersed in a
FIGURE 5.5.2
solution of lead(II) nitrate?
14 Use the electrochemical series to determine whether:
Rank the half-cells in order of their reduction half-cell
potentials, from highest to lowest. a elemental iodine is an oxidising agent or a reducing
agent
b calcium metal is a strong or weak reducing agent

CHAPTER 5 | GALVANIC CELLS AS A SOURCE OF ENERGY 149


c nickel is a better reducing agent than silver series than the Fe2+(aq)/Fe(s) pair and higher
d Cu2+(aq) is a better oxidising agent than Ag+(aq) than Al3+(aq)/Al(s). Explain how the student could
e Fe2+(aq) can act as an oxidising agent and experimentally determine the relative positions of
a reducing agent. the three pairs in the series.
15 a Use the electrochemical series to predict what 23 Account for the following observations.
might be expected to occur if hydrogen gas were a Bromine reacts with iodide ions in solution but
bubbled through a solution containing Fe3+ ions. does not react with chloride ions.
b Write an equation for the predicted reaction. b Hydrogen peroxide (H2O2) solution can
c When the reactants were mixed in an experiment, spontaneously decompose to form water
no reaction was observed. Suggest possible reasons and oxygen.
for this. c Tin metal is added to solutions of tin(II) chloride to
prevent oxidation of the tin(II) ions by oxygen in air.
Everyday sources of power
d Blocks of zinc are attached to the iron hulls of ships
16 Match the following terms with their correct definition. to reduce corrosion.
Term Definition 24 A student working in the laboratory spilled an iodine
solution over the bench, causing a dark brown stain
Galvanic cell A rechargeable galvanic cell
to form. Suggest how the student could remove the
Primary cell A device that converts chemical energy iodine stain.
into electrical energy
25 What are the limitations that need to be considered
Secondary cell A non-rechargeable galvanic cell when using the electrochemical series to predict
whether or not a certain reaction will occur?
17 Explain the difference between:
26 Many of the ‘alkaline cells’ on the market contain zinc
a anode and cathode electrodes in contact with an electrolyte containing
b cell and battery hydroxide ions. The half-cell reaction might be
c discharge and recharge. represented as:
18 What feature enables secondary cells such as lithium- Zn(s) + 4OH–(aq) → Zn(OH)42–(aq) + 2e–
ion cells to be recharged? To investigate if the standard electrode potential (E°)
19 Explain what happens to the oxidising agent, reducing of these half-cells is the same as that of a half-cell
agent, anode and cathode when a secondary cell is reaction using a zinc electrode in contact with a zinc
switched from discharge to recharge. nitrate electrolyte (for which the electrode reaction
20 Mains electricity costs about 5 cents per MJ of energy, would be Zn(s) → Zn2+(aq) + 2e–), a student was
or less, depending on the tariff. The cost of the same provided with the two half-cells shown in Figure 5.5.3,
amount of electrical energy produced by a cell is far as well as a Cu2+(aq)/Cu(s) half-cell.
more—about $1300 for a dry cell and even more for a Zn Zn Cu
button cell. Why are people prepared to use cells and
pay such relatively high prices for electricity?

Connecting the main ideas


21 Fill in the blanks in the following passage about
galvanic cells.
The redox reaction occurring in a galvanic cell takes
place in two _______________. The electrode at which
oxidation occurs is called the _______________, Zn(OH)42–(aq) Zn2+(aq) Cu2+(aq)
whereas the other electrode where reduction occurs FIGURE 5.5.3
is the _______________. The polarity of the anode 2+

is _______________ and the polarity of the cathode


is _______________. a Write a net equation for the reaction in a galvanic
Galvanic cells can be classified as either primary cells, cell in which the ‘alkaline zinc half-cell’ is connected
which _______________ be recharged, or secondary to the Cu2+/Cu half-cell.
cells, which _______________ be recharged. b Carefully explain how the student could use the
The life of commercial cells and batteries decreases half-cells that were provided to determine whether
as temperature _______________ and the extent of the two different half-cells containing zinc had the
_______________ reactions increases. same E° value. Include fully labelled diagrams with
22 A student was told that the redox pair your answer and explain how the results could
Mn2+(aq)/Mn(s) is lower in the electrochemical be interpreted.

150 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHAPTER

Fuel cells as a source


of energy
Around the world, governments, businesses and academic institutions are
spending millions of dollars to develop and produce fuel cells. A fuel cell is a
type of galvanic cell that generates electricity from redox reactions quietly and
efficiently, and with almost no pollution. Almost the only products from a fuel
cell powered by hydrogen are electricity, heat and water.
Fuel cells were invented in 1838. The National Aeronautics and Space
Administration (NASA) was the first organisation to use fuel cells to generate power
for satellites and space capsules. Today, fuel cells provide energy for forklifts,
buses and cars, and act as a source of primary and back-up power for buildings
and communities.
Fuel cells are an important component of a vision of a future called the ‘hydrogen
economy’, in which hydrogen could become the major source of energy and
replace fossil fuels. Major technological and cost breakthroughs are needed before
a hydrogen economy can become a reality and there is dispute among scientists
over its viability.
In this chapter, you will learn how fuel cells operate. You will also learn about some
of the issues associated with the supply, storage and use of hydrogen in fuel cells.

Key knowledge
• The common design features of fuel cells including the use of porous
electrodes for gaseous reactants to increase cell efficiency (details of specific
cells not required)
• The comparison of the use of fuel cells and combustion of fuels to supply
energy with reference to their energy efficiencies (qualitative), safety, fuel
supply (including the storage of hydrogen), production of greenhouse gases
and applications
• The comparison of fuel cells and galvanic cells with reference to their
definitions, functions, design features, energy transformations, energy
efficiencies (qualitative) and applications

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


6.1 Continuous sources of electrical
energy
Fuel cells use the chemical energy of hydrogen or other fuels to cleanly and
efficiently generate electricity. Even though fuel cell technology is still being
developed, fuel cells can be used in numerous applications. These uses include as a
source of power for transport (see Figure 6.1.1) and for emergency back-up power
applications.
A fuel cell is a type of galvanic cell but, unlike the cells you studied in Chapter 5,
fuel cells do not run down or need recharging. Electricity is available for as long as
fuel is supplied to them.
In this section, you will learn about how fuel cells operate, their advantages, and
some of the challenges scientists face in bringing the potential of their use to reality.

FUEL CELLS
The major limitation of the cells that have been examined so far is that they contain
relatively small amounts of reactants. Furthermore, when the reaction reaches
equilibrium, the cell must be discarded or recharged.
Cells can be constructed in which the reactants are supplied continuously,
allowing constant production of electrical energy. These devices are called fuel cells.

A key difference between a fuel cell and a primary or secondary cell is that the
reactants are not stored in the fuel cell. They must be continuously supplied from
an external source.
FIGURE 6.1.1 A hydrogen fuel cell for an electric
bicycle. The hydrogen bicycle operates like a
standard electric bicycle, but the battery lasts
three times longer.
Fuel cells transform chemical energy directly into electrical energy, enabling efficient
use of the energy released by spontaneous redox reactions. They are a useful source
of continuous electricity and could be used to provide energy for vehicles, buildings
and even cities. Energy losses such as those that occur in coal-fired power stations
and combustion engines are avoided, with a consequential reduction in the volume
of greenhouse gases produced.
Fuel cells are generally quoted as being 40–60% efficient, compared with
efficiencies of 30–40% for thermal power stations and 25–30% for car engines,
which involve a series of different energy transformations.
In addition, modern fuel cells use the waste heat that they produce to make
steam. This steam can be used for heating or to operate a turbine, thus raising the
efficiency of the cells to up to 85%.

chemical energy is directly converted into electrical energy.

Some scientists predict that, in the future, hydrocarbons will be replaced by


hydrogen as the principal source of energy for transport and other purposes (the
hydrogen economy). This would mean a drastic reduction in the production of
greenhouse gases and other pollutants without affecting your quality of life. In the
hydrogen economy, fuel cells are seen as a replacement for the internal combustion
engine.
A fuel cell using hydrogen as a fuel produces electricity, water, heat and very
small amounts of nitrogen dioxide and other emissions.

152 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Although the basic principles behind the operation of a fuel cell were discovered
in 1838, it was not until the 1950s that fuel cells were used for small-scale power
production. Fuel cells, such as the one shown in Figure 6.1.2, were the main
on-board power supply units and source of water during the Apollo space program
that put humans on the Moon. An explosion in a fuel cell was responsible for the
failure of the Apollo 13 mission.

Figure 6.1.3 shows a simplified diagram of the key parts of a hydrogen–oxygen


fuel cell. The fuel cell has two compartments: one for the hydrogen gas and the
other for the oxygen gas. The gas compartments are separated from each other
by two porous electrodes and an electrolyte solution. The electrode at the
hydrogen compartment is the anode; the electrode at the oxygen compartment is
the cathode.

‒ +

electrolyte

hydrogen gas inlet oxygen gas inlet FIGURE 6.1.2


supply electricity for the Apollo space program

later space shuttles.

porous cathode
porous anode

water outlet
FIGURE 6.1.3

The type of fuel cell used in the Apollo program used potassium hydroxide
solution as the electrolyte and the cell operated at about 250°C. Because the fuel
cell uses potassium hydroxide for the electrolyte, it is commonly referred to as an
alkaline fuel cell. Alkaline fuel cells are still used in the space program today.
• At the anode (–), hydrogen gas (the ‘fuel’) is oxidised by reacting with hydroxide
ions from the electrolyte:
H2(g) + 2OH–(aq) → 2H2O(l) + 2e–
• At the cathode (+), oxygen gas is reduced:
O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
The overall equation for the reaction is:
2H2(g) + O2(g) → 2H2O(l)
Each cell produces about 1 volt. Higher voltages are obtained by connecting
a number of fuel cells in series to form a battery or fuel cell stack. The only
by-products are water and heat.

CHAPTER 6 | FUEL CELLS AS A SOURCE OF ENERGY 153


A range of different fuel cells has been developed, using different electrolytes,
electrodes and operating temperatures, as shown in Table 6.1.1.

TABLE 6.1.1

Fuel cell Electrolyte Efficiency (%) Operating Application Typical half-equations


temperature (°C)

Alkaline fuel Potassium 60 90–100 Space vehicles Anode:


cell hydroxide H2(g) + 2OH–(aq) → 2H2O(l) + 2e–
Cathode:
O2(g) + 2H2O(l) + 4e– → 4OH–(aq)

Methanol fuel Polymer 40 50–100 Mobile phones Anode:


cell membrane Laptop CH3OH(l) + H2O(l) → CO2(g) + 6H+(aq) + 6e–
computers Cathode:
4H+(aq) + O2(g) + 4e– → 2H2O(l)

Molten Molten lithium, 50–60 600–1000 Electricity utility Anode:


carbonate sodium or H2(g) + CO32–(l) → H2O(l) + CO2(g) +2e–
fuel cell potassium Cathode:
carbonates O2(g) + 2CO2(g) + 4e– → 2CO32–(l)

Phosphoric Liquid 40–45 175–200 Electricity utility Anode:


acid fuel cell phosphoric Transportation H2(g) → 2H+(aq) + 2e–
acid Cathode:
O2(g) + 4H+(aq) + 4e– → 2H2O(l)

Proton Solid 60 60–100 Portable power Anode:


exchange polyperfluoro Transportation H2(g) → 2H+(aq) + 2e–
membrane sulfonic acid Cathode:
fuel cell O2(g) + 4H+(aq) + 4e– → 2H2O(l)

Solid oxide Solid 50–60 600–1000 Electricity utility Anode:


fuel cell zirconium H2(g) + O2–(s) → H2O(l) +2e–
oxide Cathode:
O2(g) + 4e– → 2O2–(s)

The nature of the electrodes is crucial to the efficiency of a fuel cell. The
electrodes must be both conducting and porous to allow the hydrogen and oxygen
to come into contact with the ions in the electrolyte and to allow the redox half-
reactions to occur at their surface. The size of the current that can be drawn from a
fuel cell depends on the surface area of the electrodes.
Catalysts are employed to enhance the rate of reaction and the current that
can be produced from a cell. The catalyst incorporated in the anode increases the
rate of oxidation of the fuel gas. Platinum metal is commonly used as a catalyst
at this electrode. The cathode catalyst, which increases the rate of the reduction
half-reaction, can be made from a different material, such as nickel powder or a
nano-material.

Fuels cells contain porous electrodes that allow reactants to diffuse through
them to react with ions in the electrolyte. They often contain catalysts to

The electrolyte in a fuel cell carries ions from one electrode to the other.
Different electrolytes have been employed in fuel cells, including:
• aqueous alkaline solutions, usually KOH
• liquids such as phosphoric acid (H3PO4)
• molten carbonate salts, such as Na2CO3 or MgCO3
• permeable polymer membranes, which only allow the passage of positive ions
• ceramics, made from oxides of metals such as calcium and zirconium.

154 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHEMFILE
Fuel cells around us
Some types of breathalysers use fuel cell technology to measure
blood alcohol levels. In this fuel cell, ethanol is oxidised and
the electricity generated indicates the blood alcohol level

Fuel cells are also found in nature. The electric eel, which grows

each cell is the food consumed by the eel and the oxidising

FIGURE 6.1.5
pulses of electrical discharge are emitted by the eel and then bounce
back from passing objects to be detected by special electroreceptors

intensity electrical discharges can also be used to stun or kill prey or


FIGRUE 6.1.4

HYDROGEN—A FUEL FOR FUEL CELLS


Although fuel cells can be designed to use a range of different fuels, most are
designed to use hydrogen. The widespread use of hydrogen as a source of energy
presents special challenges and issues, in terms of its production, distribution,
storage and safety.

A fuel cell using hydrogen can be described as a ‘zero-emission’ device because


water is almost the only product apart from electricity and heat. However, unless
the hydrogen fuel is produced using renewable energy, the production of hydrogen
can result in significant levels of greenhouse gases and other pollutants. To some
extent, this negates the benefits of the use of fuel cells.
At present, almost 95% of hydrogen is produced from fossil fuels, such as natural
gas, oil and coal through the process of steam reforming. In this process, steam
reacts with the fossil fuel at high temperature in the presence of a nickel catalyst.
The reaction for methane is represented by:
Ni
CH4(g) + H2O(g) CO(g) + 3H2(g)
The carbon monoxide generated can be used to generate further hydrogen,
using a copper or iron catalyst:
CO(g) + H2O(g) Cu or Fe CO2(g) + H2(g)
The hydrogen produced by steam reforming has a lower energy content than
the original fuel, as some of the original chemical energy is lost as waste heat during
production. Furthermore, steam reforming leads to carbon dioxide emissions, in
the same way as the use of the fossil fuel in a power station or car engine would do.
It is argued that hydrogen generated in this way would still be cleaner overall than
fossil fuels due to the higher efficiency of fuel cells.
Advocates of the use of steam reforming for generating hydrogen for fuel cells
also suggest that, because the carbon dioxide is produced at the site of the steam-
reforming process, it could be possible to capture the greenhouse gas at its source
and store it, preventing its release to the atmosphere.
CHAPTER 6 | FUEL CELLS AS A SOURCE OF ENERGY 155
At present, there are only two practical methods of generating hydrogen without
producing carbon dioxide.
• Using electrical energy to convert water to hydrogen. Electricity can be generated
from renewable sources such as solar-power farms and wind farms. (You will
look at the chemical principles involved in the process of converting electrical
energy to chemical energy in Chapter 9.)
• Collecting biogas from landfill sites and converting the methane in the gas to
hydrogen by steam reforming.

Widespread adoption of hydrogen as the primary fuel (for powering vehicles


and providing electricity for industrial and domestic applications) would require
massive expenditure on infrastructure. Changes to pipelines and filling stations, as
well as improvements in hydrogen storage methods, would be required. Figure 6.1.6
shows a vision for the future use of hydrogen.

residential and
national commercial buildings
grid or end users
fuel cell
unit
direct domestic appliances and
electricity small business applications
back-up
fuel cell

H2
wind solar
H2 portable fuel
hydrogen cell unit
tanks portable
high-volume, applications
long-term storage

hydrogen generator
(electrolysis of water)

hydroelectric dam fuel cell


hydrogen
automobile

FIGURE 6.1.6

Although hydrogen has a very high energy content by mass (143 kJ g–1) compared
with fuels such as petrol (44 kJ g–1), there are issues with storage, particularly within
vehicles. This is because hydrogen is a gas at room temperature.
The established methods of hydrogen storage in cars, trucks and buses are as
liquid hydrogen or compressed hydrogen.
• Liquid hydrogen. Liquid hydrogen boils at the extremely low temperature of
–252°C and a considerable quantity of energy is needed to liquefy it. The tanks
used to store liquid hydrogen must be well insulated. The energy available per
litre of liquid hydrogen (8  MJ L–1) is about four times less than for a liquid
hydrocarbon fuel such as petrol (32 MJ L–1), so a vehicle using liquid hydrogen
requires a much larger fuel tank to achieve the same driving range.
• Compressed hydrogen. Hydrogen can be stored in high-pressure tanks (up to
700 bar pressure). A  high-pressure hydrogen storage tank needs to be larger
to store the same amount of energy as a liquid hydrogen tank. In fact, using
currently available high-pressure technology, a high-pressure tank would need
to be larger than the boot of a typical car to effectively replace a standard
hydrocarbon fuel tank.

156 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Scientists are investigating alternative methods of storing hydrogen, known
generally as materials-based storage (see Figure 6.1.7), which offer considerable
promise but require further development.
• Hydrogen can adsorb to the surface of materials such as metal hydrides, either
as hydrogen molecules or as hydrogen atoms.
• Hydrogen can also dissociate and be absorbed into the lattice structure of
some solid materials.
• Hydrogen can react reversibly with a range of different chemicals.
By these means, it may be possible to store hydrogen in smaller volumes at low
pressure and at temperatures close to room temperature.

(a) (b)

FIGURE 6.1.7

Hydrogen is generally regarded as a more dangerous fuel than hydrocarbon fuels


such as petrol. Hydrogen burns readily and a flame or spark will ignite almost any
combination of hydrogen and air. An explosion, rather than merely a flame, is the
likely outcome.
On the other hand, the low density of hydrogen means that, if a leak occurs,
hydrogen rises rapidly and quickly disperses in ventilated areas, often without
ignition. In fact, a fire in a hydrogen-powered vehicle can be less damaging than a
fire in a petrol-powered vehicle.
The use of hydrogen poses unique safety challenges. Strict codes and standards FIGURE 6.1.8
will be required for its use, including the need for hydrogen sensors to detect leaks.
A number of studies have concluded that, while there are different safety concerns,
hydrogen is no more dangerous than petrol. Experts predict that, in the future,
engine.
hydrogen will be used as a fuel with at least the same level of safety and convenience
as today’s hydrocarbon fuels.

APPLICATIONS OF FUEL CELLS


Most major vehicle manufacturers are investigating the use of fuel cells as an
alternative to the internal combustion engine, given that fuel cells have better fuel
efficiency and lower emissions of greenhouse gases and other pollutants. Also, fuel
cells do not rely on oil (Figure 6.1.8).
Aside from their use in transport, the use of fuel cells is small at present but
growing rapidly.
• A 1.3 MW power plant in Italy is a phosphoric acid fuel cell that uses hydrogen
from steam reforming of natural gas as its fuel source (Figure 6.1.9).
• A 59 MW power plant began operation in South Korea in 2014, providing
FIGURE 6.1.9 Interior of the PRODE fuel cell
power and heat for local homes.
• One supermarket chain in the United States has ordered fuel cells to power its
fleet of 1700 forklifts. the fuel and phosphoric acid as the electrolyte.
• Silicon Valley technology companies in California, USA, are installing fuel cells
as a stable, sustainable source of power.

CHAPTER 6 | FUEL CELLS AS A SOURCE OF ENERGY 157


EXTENSION

Redox flow batteries


An interesting type of fuel cell under development is the A redox flow battery can be recharged by applying
redox flow battery, which has the potential of cheaper an opposite voltage to the cell, which causes the reverse
energy storage than devices such as lead–acid batteries. cell reaction to occur. Alternatively, for a rapid recharge,
As shown in Figure 6.1.10, a redox flow battery has the spent solutions can be replaced with a new batch
two separate compartments of solutions containing the of solutions.
reactants. A wide range of different reactants has been Although these batteries could provide cheaper energy
used in experimental cells. The solutions are pumped into storage, their storage tanks, pumps and flow control units
the cell from storage tanks. A membrane between the add to their weight and make their operation complicated.
compartments allows exchange of ions while preventing
contact between the two solutions.

– +
electrode

electrode
solution solution
of reducing of oxidising
agent agent

membrane
pump pump
for ion
exchange
FIGURE 6.1.10

ADVANTAGES AND DISADVANTAGES OF FUEL CELLS


Scientists are striving to reduce the overall costs of fuel cells and to improve the
electric current that can be drawn from them by increasing the rate of reaction at
the electrodes. As described above, various types of fuel cells have been developed
and tested, using a number of different fuels, electrolytes and catalysts.
Table 6.1.2 lists some of the advantages and disadvantages of fuel cells.

TABLE 6.1.2

Advantages Disadvantages

• Fuel cells convert chemical energy directly to electrical energy. • Fuel cells require a constant fuel supply.
This is more efficient than the series of energy conversions that • Fuel cells are expensive. They are still a developing technology,
takes place in power stations that burn fossil fuels: chemical and are not being made in large numbers so there are no
energy → heat energy → mechanical energy → electrical energy. economies of scale as there are in other industries.
• Hydrogen fuel cells produce water and heat as by-products. No • Some types of fuel cell use expensive electrolytes and catalysts.
greenhouse gases, such as carbon dioxide, are released. • The use of fuel cells in transport will require an extensive network
• Fuel cells will generate electricity as long as the fuel is supplied. of hydrogen filling stations before it can become widespread.
Conventional batteries need to be recharged or replaced. • Fuel cells generate a direct current (DC); electrical appliances
• Fuel cells can use a variety of fuels. used in the home and in industry rely on an alternating
• Electricity can be generated on-site and users are not reliant current (AC). An inverter is required to change DC to AC at the
on connection to an electricity grid. Waste heat can be used to appropriate voltage.
heat water for a hot water system or provide heating for a home • At present, the hydrogen used in many fuel cells is mainly
during winter. sourced from fossil fuels. This process involves energy losses and
generates greenhouse gases.
• There are significant issues associated with the storage and safety
of hydrogen fuel.

158 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
COMPARING FUEL CELLS AND PRIMARY AND
SECONDARY CELLS
A fuel cell is a type of galvanic cell in which the reactants are supplied continuously.
Unlike the primary cells and secondary cells described in Chapter 5, which
can produce power for only a limited time until their reactants are depleted, in a
fuel cell the reactants (a combustible fuel and oxygen or air) are constantly entering
the cell and products are being removed.
Primary and secondary cells and fuel cells are compared in Table 6.1.3.

TABLE 6.1.3

Primary and secondary cells Fuel cells

Definition A primary or secondary cell A fuel cell is a galvanic cell that


is a type of galvanic cell, or converts the chemical energy of a
voltaic cell. These galvanic cells fuel into electrical energy. The fuel
are electrochemical cells that and air or oxygen are supplied
convert chemical energy from continuously.
spontaneous redox reactions in
the cell into electrical energy.
The reactants in primary and
secondary cells are contained
within the galvanic cell.
As a consequence, primary and
secondary cells can produce
power for only a limited time
until their reactants are depleted.

Function To produce electrical energy; they To produce electrical energy;


are particularly useful as a source they are particularly useful as a
of portable electrical energy. continuous source of high electric
current for both portable and
fixed applications.

Design features • Oxidation occurs in one part • Two separate compartments


of the cell and reduction are present: one for inflow of a
in another. combustible gaseous fuel (at the
• An oxidation half-reaction negatively charged anode) and
occurs at the negatively the other for oxygen or air (at
charged anode. the positively charged cathode).
• A reduction half-reaction • An oxidation half-reaction
occurs at the positively charged occurs at the negatively
cathode. charged anode.
• A salt bridge composed of • A reduction half-reaction
an electrolyte carries charge occurs at the positively charged
between the electrodes. cathode.
• Electrodes are porous to allow
contact between reactant gases
and the electrolyte.
• Catalysts are used to increase
cell efficiency.
• An electrolyte carries charge
between the electrodes.

Energy Chemical to electrical Chemical to electrical


transformations

Energy 60–90% (high compared with 40–60% efficient; up to 85% if


efficiencies energy efficiency of power heat produced by the cell is also
stations and hydrocarbon- used to generate electricity.
powered cars).

Typical Primary cells: energy for watches, Cars, buses, commercial


applications remote controls, portable radios, electricity generation, emergency
cameras, heart pacemakers and back-up power supplies
hearing aids
Secondary cells: cars, mobile
phones, cameras, computers,
power tools

CHAPTER 6 | FUEL CELLS AS A SOURCE OF ENERGY 159


6.1 Review
SUMMARY

• Fuel cells are a type of galvanic cell, converting • The emissions of greenhouse gases from a fuel
chemical energy directly into electrical energy. cell are much less than if the fuel were burnt in
• Fuel cells are devices in which the reactants (usually a power station or internal combustion engine.
gases) are supplied continuously, allowing constant • Some scientists predict that fuel cells will play a
production of electrical energy. key role in the transition from a dependence on
• The electrodes used in fuel cells allow direct contact fossil fuels for energy to a hydrogen economy.
between the gases and electrolyte. They have a high • The widespread use of hydrogen as a source of
surface area and are porous to ensure high cell energy presents special challenges and issues,
efficiency. Catalysts are often part of an electrode in terms of its production, distribution, storage
to increase the rate of reaction. and safety.
• Electricity generation using fuel cells is more
efficient than if the electricity were generated by
the combustion of the same fuel.

KEY QUESTIONS

1 Which one of the following is a correct statement 4 An experimental fuel cell that uses methanol as the
about what happens in a hydrogen–oxygen fuel cell. fuel has the half-equations:
A Hydrogen gas is oxidised at the anode. CH3OH(g) + 6OH–(aq) → CO2(g) + 5H2O(l) + 6e–
B Electrons flow through the external circuit from O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
cathode to anode. a Write the equation for the overall cell reaction.
C Solid, impermeable electrodes are required b Which reaction occurs at the positive electrode
to prevent contact between reactants and of the cell?
the electrolyte. c Suggest a suitable electrolyte for the cell.
D Oxygen gas is oxidised at the anode. d When the cell begins to produce electricity, the pH
2 Which one or more of the following features do of the electrolyte near the cathode increases and
secondary cells and fuel cells have in common as eventually reaches a constant value. Explain why
they produce electricity? this occurs.
A A catalyst is used to increase reaction rate. e Electricity could be obtained from thermal energy
B Cations in the electrolyte move towards produced by combustion of methanol. What is
the cathode. the main advantage of using a fuel cell to produce
C The anode is negative. electricity?
D The cathode is constructed from a porous material. 5 Why is large-scale production of electricity using fuel
E Oxidation occurs at the cathode. cells suggested as part of a solution to the greenhouse
F The oxidising agent is a gas. problem?
G Chemical energy is converted into electrical energy.
3 Hydrogen gas and oxygen gas are reacted in a
phosphoric acid fuel cell, which is a type of fuel cell
that uses liquid phosphoric acid as an electrolyte.
a Write equations for the half-reactions that occur
at the anode and cathode.
b Based on the two half-equations from part a,
determine the overall cell equation for this reaction.

160 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
Chapter review
KEY TERMS

absorb electrode primary cell


adsorb electrolyte secondary cell
anode fuel cell steam reforming
biogas galvanic cell voltaic cell
cathode hydrogen economy
electrochemical cell materials-based storage

Continuous sources of electrical energy d Fuel cell vehicles fitted with a tank of liquid
1 Which one of the following reactions might be used as hydrogen can travel up to four times further than
the basis for an experimental fuel cell? fuel cell vehicles fitted with petrol tanks of the
A 2CO(g) + O2(g) → 2CO2(g) same size.
B 2NO2(g) → N2O4(g) e Hydrogen stored under pressure can provide the
C HCl(g) + NH3(g) → NH4Cl(s) same energy per litre as hydrocarbon fuels.
D CO2(g) + H2O(l) → H2CO3(aq) 6 Select the correct answer from the options given in
bold to complete the following paragraphs, which
2 Which one of the following statements best describes
summarise information about fuel cells.
the role of the electrolyte in a fuel cell?
A It allows positive charges to accumulate in one Fuel cells convert chemical/electrical energy
half-cell and negative charges to accumulate in to chemical/electrical energy and are a type of
the other. galvanic cell. At the anode, the fuel/oxidising agent
B It allows direct contact of the fuel from the anode undergoes oxidation/reduction whereas at the
to mix with the oxidising agent from the cathode. cathode the fuel/oxidising agent is oxidised/reduced.
Energy is supplied constantly if reactants/products
C It allows movement of ions to balance charges
are available.
formed at the electrodes.
D It provides a pathway for electrons to move The nature of the electrodes is critical to the operation
between the half-cells. of the fuel cell. Electrodes must conduct electricity,
catalyse the reaction and allow contact between the
3 Which one of the following substances is least likely
electrolyte/oxidising agent and the fuel and the
to be found as a reactant at the anode of a fuel cell?
electrolyte/fuel and the oxidising agent. There must
A CH3OH
be controlled contact / no direct contact between
B CO2 the fuel and the oxidising agent.
C H2
Electricity generation using fuel cells is more/less
D CH4
efficient than if the electricity were generated by
4 Which one of the following is not being considered the combustion of the same fuel. The emissions of
as a means of storing hydrogen for use in fuel cells? greenhouse gases from a fuel cell are much less/
A Adsorbed to the surface of metal hydrides significantly greater than if the fuel were burnt in a
B As pure solid hydrogen power station or internal combustion energy.
C As pure compressed hydrogen While hydrogen–oxygen fuel cells are a clean energy
D As pure liquid hydrogen source producing only energy and water /oxygen,
5 Indicate whether the following statements about the the production, storage, distribution and safety of
generation, storage and safety of hydrogen are true hydrogen/water are challenging issues.
or false.
a Most of the hydrogen produced in the world is
generated from fossil fuels.
b Hydrogen is regarded by scientists as almost twice
as dangerous a fuel for vehicles as petrol.
c Hydrogen can be stored by adsorption onto metal
hydrides.

CHAPTER 6 | FUEL CELLS AS A SOURCE OF ENERGY 161


7 Label the diagram of a hydrogen–oxygen fuel cell in a Write a half-equation for the reaction that occurs
Figure 6.2.1. at the negative electrode of the fuel cell.
b If the fuel cell operates under standard conditions,
what is the maximum voltage that could
polarity of polarity of
electrode: electrode: be generated?
11 A fuel cell uses methanal gas (HCHO) as a fuel and
oxygen gas as the oxidising agent. It uses an alkaline
electrolyte and operates at 70°C.
a Write the equation for the overall cell reaction.
b What is the half-equation for the cathode reaction?
(g) inlet (g) inlet

porous anode
Connecting the main ideas
porous cathode 12 An Australian company developed a ceramic fuel cell.
Instead of a liquid electrolyte, the cell uses a ceramic
electrolyte through which oxide ions (O2–) can move.
The fuel cells are designed so that the fuel and air are
directed separately onto the appropriate electrode.
water outlet The diagram in Figure 6.2.2 represents a ceramic fuel
FIGURE 6.2.1 cell that uses methane gas (CH4) as the energy source.
The electrode reactions are:
8 Decide whether the following statements apply to O2(g) + 4e– → 2O2–(s)
fuel cells, primary cells or secondary cells. Some CH4(g) + 4O2–(s) → CO2(g) + 2H2O(g) + 8e–
statements apply to all types of cells.
a Convert chemical to electrical energy.
b Oxidation occurs at the anode and reduction occurs waste gases
(CO2, H2O) depleted air
at the cathode.
c The anode is the negative electrode as the cell
generates electricity.
d Recharged by connecting to a power supply.
e Electrode reactions occur in separate compartments.
electrolyte
f Chemical energy is stored within the cell. X O2– Y
g Reactant is supplied constantly.
9 A fuel cell is used as a breathalyser to detect the
presence of alcohol in a motorist’s breath.
The equation for the cell reaction is:
fuel, CH4 air
CH3CH2OH(g) + O2(g) → CH3COOH(aq) + H2O(l)
In this reaction, ethanol (CH3CH2OH) is oxidised to FIGURE 6.2.2 A ceramic fuel cell.
ethanoic acid (CH3COOH) and oxygen is reduced a Write an overall equation for the reaction that
to water. occurs in this ceramic fuel cell.
a Write an equation for the half-reaction that occurs b Identify electrodes X and Y as the cathode or
at the anode. the anode.
b Write an equation for the half-reaction that occurs c Explain the claim that this method of generating
at the cathode. electricity will reduce carbon dioxide emissions,
c As the cell operates, will cations in the electrolyte by comparison with a power plant that burns
move towards the anode or the cathode? natural gas (containing methane) and uses the heat
d Explain whether the fuel cell will generate a voltage released to boil water and then generate electricity.
if natural gas, which contains mostly methane,
13 Consider the similarities and differences between a
is blown into the breath inlet.
primary cell and a fuel cell.
10 An experimental fuel cell uses methane as the a List the design features that the two types of cells
source of energy. The relevant half-equations in the have in common.
electrochemical series are: b List the design features that are different in the two
CO2(g) + 8H+(aq) + 8e– CH4(g) + 2H2O(l) types of cells.
E° = +0.17 V
14 ‘Hydrogen–oxygen fuel cells are the energy source of
O2(g) + 4H+(aq) + 4e– 2H2O(l)
the future.’ Discuss the advantages and disadvantages
E° = +1.23 V
of an energy supply based on these fuel cells.

162 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
UNIT 3 • Area of Study 1
REVIEW QUESTIONS

What are the options for energy production?


Multiple-choice questions The following information relates to Questions 5–7.
1 Which of the following is not an example of using Biodiesel manufactured from plant oils is an increasingly
the energy obtained from a fuel to produce electrical important alternative to the petrodiesel isolated from crude
energy? oil. One issue with the use of biodiesel is that it has a
higher affinity for water than petrodiesel, and consequently
A Production of electricity in a methanol fuel cell
has a higher water content. However, the potential
B Production of electricity in a wind turbine
reduction in net greenhouse emissions of switching to
D Production of electricity in a coal-fired power plant biodiesel makes it very attractive.
D Production of electricity in a nuclear power plant
5 The reason for the higher affinity of biodiesel for water
2 Which of the following is not characteristic of a reaction is that:
in which energy is obtained from a fuel? A molecules in biodiesel possess polar functional
A It is exothermic. groups that enable bonding to water molecules
B Chemical energy (enthalpy) is converted into other B biodiesel is ‘natural’ and natural things always have
forms of energy. an affinity for water
C The combined enthalpy of the products is higher C the water is removed from petrodiesel in the refining
than that of the reactants. process
D The enthalpy change (∆H) is negative. D the larger molecules in biodiesel are able to form
3 Which of the following equations correctly represents more bonds to water molecules.
the complete combustion of ethanol? 6 The use of biodiesel in cold climates can be
A CH3CH2OH(l) + O2(g) → 2C(s) + 3H2O(g) problematic because:
B CH3CH2OH(l) + 2O2(g) → 2CO(g) + 3H2O(g) A at low temperatures the molecules in biodiesel
C CH3CH2OH(l) + O2(g) → CH3COOH(l) + H2O(g) undergo decomposition
D CH3CH2OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g) B unburnt fuel can clog the exhaust systems of motor
4 Two gaseous fuels that have been investigated as vehicles
possible alternative energy sources are hydrogen gas, C combustion of biodiesel at low temperatures
(H2) and biogas, which comprises mostly methane increases greenhouse gas emissions
(CH4). The table below shows the energy released D its higher viscosity can cause fuel line blockages.
by the combustion of 1 mol of hydrogen and 1 mol 7 The difference in the amount of carbon dioxide
of methane. generated by the combustion of petrodiesel and
Fuel Equation for combustion Energy released biodiesel is very small, yet it is argued that switching to
reaction per mole of fuel biodiesel will reduce net greenhouse emissions. This is
(kJ mol–1) mainly because:
1 A growing plant feedstocks for biodiesel production
Hydrogen H2(g) + O (g) → H2O(g) 242
2 2 removes carbon dioxide from the air through
CH4(g) + 2O2(g) → photosynthesis
Methane 802
CO2(g) + 2H2O(g)
B the carbon dioxide produced by burning fossil
Consider the following situations that may apply to the fuels is a stronger greenhouse gas than the carbon
use of the fuels. dioxide produced by burning biofuels
I Limiting greenhouse gas emissions is very C combustion of biodiesel produces fewer other
important. greenhouse gases, such as methane
II Equal masses of the two gases are to be stored. D biodiesel combustion produces significantly more
III Equal volumes of the gases are to be stored (at the energy so less needs to be burnt for the same
same temperature and pressure). energy output.
Hydrogen gas would be the preferred fuel in which
situation(s)?
A I, II and III B I and II
C II and III D I only

REVIEW QUESTIONS 163


UNIT 3 • Area of Study 1

Refer to the following equation for the reaction between B


hydrochloric acid and ammonia solution when answering
Questions 8 and 9. 2220 kJ mol–1
HCl(aq) + NH3(aq) → NH4Cl(aq) ∆H = –52 kJ mol–1

Enthalpy
8 The reaction is:
A endothermic, because the energy involved in bond
forming is more than that involved in bond breaking
B endothermic, because the energy involved in bond
forming is less than that involved in bond breaking
C exothermic, because the energy involved in bond C
forming is more than that involved in bond breaking
D exothermic, because the energy involved in bond
forming is less than that involved in bond breaking.

Enthalpy
9 Which of the following happens when hydrochloric 2220 kJ mol–1
acid and ammonia solutions are allowed to react in a
perfectly insulated container?
A The total energy inside the container decreases.
B The total energy inside the container increases.
C The total energy inside the container is unchanged D
but there is less enthalpy (chemical energy) after
the reaction.
D The total energy inside the container is unchanged
Enthalpy

but there is more enthalpy (chemical energy) after


2220 kJ mol–1
the reaction.
The following information relates to Questions 10–12.
As a response to rising petrol prices, the Australian
Government in 2006 offered car owners a $2000 incentive
to convert their cars from petrol to LPG. Propane is one of
the gases in the mixture sold as LPG. The thermochemical 11 When 10.0 g of propane undergoes complete
equation for the complete combustion of propane is: combustion:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) A 5.05 × 103 kJ of energy is absorbed
∆H = −2220 kJ mol−1 B 5.05 × 103 kJ of energy is released
10 Which energy profile diagram best represents the C 3.92 × 101 kJ of energy is absorbed
energy changes that take place during this reaction? D 3.92 × 101 kJ of energy is released.
A 12 When 1 MJ of energy is released in this reaction, the
volume of CO2(g) produced, at standard laboratory
conditions (SLC), is:
2220 kJ mol–1 A 3.35 × 104 L B 33.5 L
Enthalpy

C 1.12 × 10  L
4
D 11.2 L
13 Given that the density, d, of a substance is given by the
m
formula d = and that M represents molar mass, then
V
the density of any gas is given by which formula?
R×T
A d=
p×M
p
B d=
R×T×M
R×T×M
C d=
p
p×M
D d=
R×T

164 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
14 Which of the following lists species arranged with 19 An electrochemical cell was made by dipping a copper
the nitrogen atoms in order of increasing oxidation rod into a solution of 1 M CuSO4 in one beaker and
number? dipping a nickel rod into a solution of 1 M NiSO4 in
A NH4+, N2, NO, NO3− another beaker. The metals were connected with wire
B NO3−, NO, NH3, N2 and the two solutions were connected by a piece of
C NO2, N2, NO, HNO3 paper towel that had been soaked in a potassium
nitrate solution. The cell is shown in the following
D NO3−, NO, N2, NH3
diagram.
15 Use the electrochemical series to determine which one
of the following would not be expected to occur to an V
appreciable extent. salt bridge
+ (paper towel) –
A 2H+(aq) + Fe(s) → Fe2+(aq) + H2(g)
B 2Ag+(aq) + Ni(s) → 2Ag(s) + Ni2+(aq) Cu Ni
C Br2(aq) + 2Fe2+(aq) → 2Br–(aq) + 2Fe3+(aq)
D 2I–(aq) + Pb2+(aq) → I2(s) + Pb(s)
16 Hydrogen gas (H2) is bubbled through a solution of NiSO4
Sn4+(aq). Which of the following observations is most CuSO4
likely?
A No reaction will occur.
B A precipitate of SnH4 will form. beaker 1 beaker 2
C The pH of the solution will decrease. The solution in beaker 1 was initially coloured blue,
D Oxygen gas will form. owing to the presence of Cu2+ ions. The solution in
17 The following equations involve ions of the transition beaker 2 was initially coloured green because of the
metal vanadium. The half-cell potential E° (V) is shown presence of Ni2+ ions. Which of the following changes
for each equation. might it be possible to detect after the galvanic cell has
V3+(aq) + e− → V2+(aq) E° = −0.25 V been discharging for a period of time?
VO2+(aq) + 2H+(aq) + e− → V3+(aq) + H2O(l) A The green colour in beaker 2 has faded and the
E° = +0.36 V mass of the copper electrode has increased.
VO2+(aq) + 2H+(aq) + e− → VO2+(aq) + H2O(l) B The blue colour in beaker 1 has faded and the mass
E° = +1.00 V of the nickel electrode has increased.
Of the ions listed, which are the strongest oxidant and C The green colour in beaker 2 has faded and the
the strongest reductant? mass of the copper electrode has decreased.
D The blue colour in beaker 1 has faded and the mass
Strongest oxidant Strongest reductant of the nickel electrode has decreased.
A VO 2
+
V2+ 20 Fuel cells provide an alternative method, often more
B VO2+ VO2+ efficient than direct combustion, of extracting energy
from the reaction between a fuel and oxygen. Which
C V3+ VO2+
of the following are the main energy transformations
D V2+ VO2+ occurring when a fuel is directly combusted, and when
reacted with oxygen in a fuel cell?
18 Which of the following best describes the features of an
anode in a galvanic cell? Direct combustion Fuel cell

Polarity Electrode reaction A enthalpy → heat electricity → enthalpy

A Positive Oxidation B heat → enthalpy electricity → enthalpy

B Positive Reduction C heat → enthalpy enthalpy → electricity

C Negative Oxidation D enthalpy → heat enthalpy → electricity

D Negative Reduction

REVIEW QUESTIONS 165


UNIT 3 • Area of Study 1

21 Much of the research advancing fuel cell technology 24 One of the boilers at a power station burns 75.6 kg of
aims at improving the catalytic effect of the electrode brown coal every second. Each kilogram of brown coal
materials. This is crucial because: produces 9.82 MJ of energy. The electrical output of
A a key limitation of fuel cells is their power output, the generator connected to this boiler is 300 MJ s–1.
which relates to the rate at which the reactions a Calculate the amount of energy produced each
can occur second by burning 75.6 kg of coal.
B it increases the total energy available from a given b Give two reasons why the answer to part a is much
quantity of reactants greater than the output of the generator.
C it reduces the output of greenhouse gases and other c Over three-quarters of the electricity generated in
wastes from the cell Victoria comes from brown coal, a non-renewable
D it allows the fuel cell reactions to be reversed, energy source. Explain what is meant by the term
making it rechargeable. ‘non-renewable energy source’.
d Many sewage treatment plants incorporate digesters
Short-answer questions that generate biogas, which can be burnt to produce
22 a Explain what is meant by the term ‘fuel’. electricity in power plants similar to Victoria’s coal-
b Methane is a useful fuel that is the major component fired ones. List some of the benefits this might
both of natural gas and of many forms of biogas. provide.
Compare these two forms of methane with respect to: 25 Consider the following thermochemical equations
i the processes that lead to their formation involving the formation of nitrogen oxides.
ii their renewability N2(g) + O2(g) → 2NO(g) ∆H = +181 kJ mol–1
iii their impact on carbon dioxide levels when used 2NO(g) + O2(g) → 2NO2(g) ∆H = –114 kJ mol–1
as energy sources. Use this information to calculate ∆H for each of the
23 Consider the following table of values of energy following equations.
available from the combustion of a range of liquid a 2N2(g) + 2O2(g) → 4NO(g)
fuels. Note that because many of these fuels are b 2NO(g) → N2(g) + O2(g)
mixtures whose composition can vary, the values 1
provided are representative only. c NO2(g) → NO(g) + O2(g)
2
d N2(g) + 2O2(g) → 2NO2(g)
Liquid fuel Typical formula Typical energy
available 26 Lighter fluid is mainly butane (molar enthalpy of
kJ g−1 kJ mL−1
combustion is –2876 kJ mol–1), which undergoes
combustion according to the following equation:
Methanol CH3OH 20 16
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g)
Ethanol CH3CH2OH 27 21 a What is the value of ∆H for the equation?
Petrol C8H18 46 33 b Sketch and label an energy-level diagram (showing
Petrodiesel C14H30 48 40 the relative enthalpies of reactants and products)
illustrating the energy changes that occur during
Biodiesel C19H38O2 38 34
this reaction.
Liquefied natural CH4 and C2H6 45 27
c Use your diagram from part b to explain why
gas (LNG)
butane does not spontaneously ignite when exposed
Liquefied petroleum C3H8 and C4H10 49 26 to air; that is, why a spark is necessary to begin
gas (LPG)
combustion.
a Identify the fossil fuels present in the table. d Calculate the heat of combustion of butane in kJ g–1.
b Identify the renewable fuels present in the table. e An inexperienced hiker wishes to use his lighter,
c What is the general relationship between the energy which contains 3.00 g of butane, to heat the water
available from each fuel and the proportion of in his mug. If his mug contains 150 mL of water
oxygen in its formula? initially at 20.0°C, and 70.0% of the heat generated
d Given the relatively low energy contents of methanol by the lighter is lost to the surroundings, what will
and ethanol, suggest reasons why their use as fuels be the temperature of the water when the fuel in the
is becoming more common. lighter is exhausted?
e Suggest one application where a fuel with a high
energy/mass ratio would be preferred.
f Suggest one application where a fuel with a high
energy/volume ratio would be preferred.

166 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
27 Many transport vehicles are fuelled by compressed 30 Hydrogen seems likely to be among the most
natural gas (CNG) rather than petrol. CNG is largely prominent of the next generation of fuels, with many
methane. The thermochemical equation for the potential applications.
complete combustion of methane is: a It is a promising replacement for traditional fossil
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) fuels in combustion engines for transport. List two
∆H = –802 kJ mol–1 advantages and two disadvantages of hydrogen as
a How much energy, in MJ, is released by the a transport fuel in combustion engines, relative to
complete combustion of 1.00 kg of methane? conventional fossil fuels.
b What volume of carbon dioxide is formed, at b Hydrogen fuel cells are also strong candidates to
standard laboratory conditions (SLC), for each MJ power electric cars in the future. List two advantages
of energy produced? and two disadvantages of hydrogen fuel cells,
c If vehicles are not properly tuned, incomplete relative to rechargeable battery technologies (such
combustion of methane can lead to the formation as lead–acid cells), for use in electric cars.
of carbon monoxide (CO). For every gram of c List one advantage and one disadvantage of
carbon monoxide produced, 18.6 kJ of energy is hydrogen fuel-cell powered electric motors relative
released. Write a balanced thermochemical equation to hydrogen combustion engines for transport.
(including ∆H) for the reaction of methane with 31 One manufacturer of direct methanol fuel cells
oxygen to produce carbon monoxide and water (DMFCs) quotes a methanol consumption rate of
vapour. 900 mL kWh (1 kWh (kilowatt hour) = 3600 kJ).
d How much energy (in kJ) is released by combustion The equation for the reaction in these fuel cells is
of one mole of methane if the percentage converted identical to that for the direct combustion of methanol
to carbon monoxide (with the balance converted to (with liquid water as a product):
carbon dioxide) is: 2CH3OH(l) + 3O2(g) → 2CO2(g) + 4H2O(l)
i 0%? ∆H = –1453 kJ mol–1
ii 20%? a Given that the fuel cell contains an acidic electrolyte,
iii 100%? write balanced half-equations for the reactions
28 A 224 L domestic hot water system running on occurring at the anode and cathode respectively.
natural gas is filled with water at 14°C and requires b Use the thermochemical equation given above to
combustion of 1.25 kg of fuel to heat the water to calculate the maximum energy (in kJ) available from
the storage temperature of 70°C (density of water is the reaction of 1.00 g of methanol with oxygen.
1.00 g mL−1). c Use the fuel consumption figure provided to
a Assuming 100% conversion, how much energy calculate the amount of electrical energy obtained
is available, in MJ kg–1, from combustion of the from the reaction of 1.00 g of methanol in the fuel
natural gas? cell (density of liquid methanol is 0.79 g mL–1).
b A typical energy value for natural gas is around d What is the percentage efficiency of conversion of
54 MJ kg–1. Account for any discrepancy with your available energy to electrical energy in the fuel cell?
answer to part a. e List some possible losses that might occur in
the fuel cell to lower the efficiency of electricity
29 A helium cylinder for the inflation of party balloons
production.
holds 25.0 L of gas, and is filled to a pressure of
16 500 kPa at 15°C. 32 For each of the following reactions:
a Express the pressure of helium gas inside the • identify them as redox or non-redox reactions
cylinder in units of: • for each redox reaction, list the changes in oxidation
i atm number occurring
ii mmHg. • for each redox reaction, identify the oxidant and
b What mass of helium does the cylinder contain the reductant.
when full? a HIO3(aq) + 3SO2(g) → 3SO3(aq) + HI(aq)
c What volume would the helium occupy at standard b SO3(g) + Ca(OH)2(aq) → CaSO4(s) + H2O(l)
laboratory conditions (SLC)? c 4Fe(OH)2(s) + 2H2O(l) + O2(g) → 4Fe(OH)3(aq)
d How many balloons can be inflated from a single d NaH(s) + H2O(l) → H2(g) + NaOH(aq)
cylinder at 30°C if the volume of one balloon is
6.5 L and each needs to be inflated to a pressure of
108 kPa?

REVIEW QUESTIONS 167


UNIT 3 • Area of Study 1

33 For each of the following unbalanced redox reactions 36 The diagram below shows a version of an alkaline
(all occurring in acidic aqueous solution) aluminium–air fuel cell being used to power a load,
• write separate balanced ionic equations for the such as an electric motor.
oxidation and reduction half-reactions
• write a balanced ionic equation for the overall air space
reaction.
cathode
a Al(s) + Br2(aq) → Al3+(aq) + Br–(aq)
b ClO–(aq) + S2O32–(aq) → SO42–(aq) + Cl–(aq)
A B
c H2O2(aq) + MnO4–(aq) → O2(aq) + MnO2(s) load
KOH(aq)
34 When a Ni–Cad cell is converting chemical energy to
electrical energy (discharge), the electrode reactions
are best described as follows.
• positive electrode: aluminium plate
NiOOH(s) + H2O(l) + e– → Ni(OH)2(s) + OH–(aq)
The half-reactions occurring are:
• negative electrode:
Al(s) → Al3+(aq) + 3e–
Cd(s) + 2OH–(aq) → Cd(OH)2(s) + 2e–
O2(g) + 2H2O(l) + 4e– → 4OH–(aq)
a Which metal, nickel or cadmium, is at the anode of
a Which arrow, A or B, shows the direction of electron
this cell as it is discharging?
flow through the load?
b Give the formula of an ionic compound that might
b What is the oxidant in this cell?
be expected to be found in the electrolyte paste of
a Ni–Cad cell. c Write a balanced equation for the overall cell
reaction.
Ni–Cad cells are superior to alkaline cells because they
can be recharged. d Explain why it is important for the cathode to
be porous.
c Explain why cells such as the Ni–Cad can
be recharged. Using a zinc (Zn) plate in place of the aluminium plate
gave a cell that still functioned. However, when a silver
d Write equations for the half-reactions and the
(Ag) plate was used instead, the cell did not function.
overall cell reaction occurring when a Ni–Cad cell
is recharged. e Account for this difference by referring to the
relative strengths of the oxidants and reductants
e Describe the energy transformation that occurs
involved.
when a Ni–Cad cell is discharging.
f Would the cell potential (voltage) produced by the
35 Referring to an electrochemical series and for each of
cell with the zinc plate be larger or smaller than
the half-cell combinations listed below, predict:
that with the original aluminium plate? Explain your
i the maximum cell voltage expected at standard answer.
conditions
g When the potassium hydroxide electrolyte was
ii which of the half-cells will contain the negative replaced with a sulfuric acid solution, the cell with
electrode the silver plate began to deliver current. Explain why
iii the ionic equation for the overall reaction changing the electrolyte made this difference.
occurring when the cell is discharging.
a Sn2+(aq)/Sn(s) and Fe2+(aq)/Fe(s)
b Fe3+(aq)/Fe2+(aq) and Al3+(aq)/Al(s)
c H+(aq)/H2(g) and I2(aq)/I–(aq)

168 AREA OF STUDY 1 | WHAT ARE THE OPTIONS FOR ENERGY PRODUCTION?
CHAPTER

Rate of chemical reactions

Chemical reactions occur at many different rates. The explosion of gunpowder and
the combustion of petrol in a car’s engine occur very quickly. On the other hand,
the weathering of buildings, the ripening of fruit and the rusting of iron all occur
quite slowly.
During chemical reactions, particles such as atoms, molecules and ions collide
with each other and undergo a rearrangement to produce new substances. It is
important to appreciate that collisions between reactant particles do not always
result in a chemical reaction. For example, while a car’s fuel tank is being filled with
petrol, the hydrocarbon molecules in the fuel are colliding with oxygen molecules
in the air without a reaction occurring.
By the end of this chapter, you will understand how rates of chemical reactions
can be measured. You will also be able to describe how varying the conditions of
chemical reactions can affect the rate of a reaction.
Using collision theory, you will learn to predict the effects of concentration of
solutions, temperature, surface area, gas pressure and the presence of a catalyst
on the rate of chemical reactions, and explain these effects.
The role of catalysts in changing the rate of chemical reactions will be considered
in relation to reaction pathways and the energy changes that occur during
reactions.

Key knowledge
• Chemical reactions with reference to collision theory, including qualitative
interpretation of Maxwell–Boltzmann distribution curves
• Factors affecting the rate of a chemical reaction, including temperature, surface
area, concentration of solutions, gas pressures and presence of a catalyst
• The role of catalysts in changing the rate of chemical reactions with reference
to alternative reaction pathways and their representation in energy profile
diagrams

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


7.1 Investigating the rate of
chemical reactions
The time it takes for a batch of chocolate brownies to cook in the oven (Figure 7.1.1)
and the time taken for a fibreglass patch on a surfboard to set are processes related
to the rate of chemical reactions.
In this section, you will learn how changes to reaction conditions affect reaction
rates.You will also learn how chemists measure the rate at which a chemical reaction
occurs.

FAST AND SLOW REACTIONS


Chemical reactions are taking place all around us:
• in the soil and rocks beneath our feet
• in the air around and above us
• inside every plant and animal
• in our homes, schools and workplaces.
FIGURE 7.1.1 How quickly do the chemical
reactions involved in baking occur? Some of these reactions are over in a flash. In a car accident when a car’s airbag
needs to be inflated, the chemical reactions producing the gas that expands the
airbag need to happen extremely quickly. On the other hand, if the car’s painted
surface is scratched to expose the metal beneath, the rusting reactions take place at
a very slow rate.

CHEMISTRY IN ACTION

Saved by a very fast chemical reaction


Imagine the scene. An 18-year-old borrows his parent’s dashboard, windscreen or front pillars, all within the blink
car to take his girlfriend for a drive to celebrate gaining his of an eye. As the head and body strike the airbags, the
driver’s licence. Roof down, enjoying the beautiful afternoon cushion of gas is forced out of the bag through tiny vents,
and the countryside, the driver rounds a corner to find the and within 100 milliseconds the bag has completely
road wet. The car begins to slide on the wet surface. In deflated.
his inexperience the driver brakes; the car starts to spin.
Suddenly, the car is leaving the road and heading straight
for a large tree. Then, bang!
Later, the car was estimated to have been travelling at
60 km/h when it hit the tree. The collision was a ‘head-
on’, with the front and passenger side taking most of the
impact. Yet the girl in the passenger seat suffered just a
chipped tooth, and her boyfriend sustained only minor
bruising.
This is the true story of a lucky escape, thanks to a
very rapid chemical reaction. As the collision took place,
airbags were inflating and then deflating as the travellers
were slammed forward towards the windscreen. The driver
described it as being ‘all over in a flash’ and had no clear
recollection of the airbags going off.
Hidden in the car’s steering wheel, dashboard and
windscreen pillars, special nylon bags fill with gas
within 30 milliseconds of impact (see Figure 7.1.2).
As a consequence, the car occupants are prevented
FIGURE 7.1.2
from smashing their heads against the steering wheel,

170 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Air bags contain a mixture of crystalline solids—sodium more nitrogen gas, as well as sodium oxide and potassium
azide (NaN3), potassium nitrate (KNO3) and silica (SiO2)— oxide, which are white powdery solids.
stored in a canister. Sensors in the front of the car detect The equation for this reaction is:
the difference between a bump and life-threatening impact. 10Na(l) + 2KNO3(s) → K2O(s) + 5Na2O(s) + N2(g)
When a response is required, an electronic impulse ‘ignites’ A filtration system prevents any of the oxides from
the sodium azide. Sodium metal and hot nitrogen gas are entering the nylon bag, while a third reaction ‘captures’
the products of this energy-releasing redox reaction: them to produce a harmless glassy solid.
2NaN3(s) → 2Na(l) + 3N2(g) In this reaction they combine with silica:
The pulse of hot nitrogen gas released from this reaction K2O(s) + 5Na2O(s) + SiO2(s) → alkaline silicate (‘glass’)
starts to inflate the nylon bag. The molten sodium metal
Chemical reactions do save lives!
immediately reduces the potassium nitrate, generating

FACTORS THAT AFFECT REACTION RATES


Experimental investigations have shown that five main factors can change the rate
of a chemical reaction:
• surface area of solid reactants
• concentration of reactants in a solution
• gas pressure
• temperature
• the presence of catalysts.
You can probably think of some examples of situations where one or more of
these conditions is changed and a reaction becomes noticeably faster or slower.

Surface area
The surface area of solid reactants can have a significant effect on reaction rate.
Smaller particles have a much larger surface area than the same mass of large
particles. As a result, the smaller particles react much faster.
Manufacturers of fireworks modify the surface area of solid reactants to
control the rate at which fuels in the fireworks burn and create different effects
(Figure  7.1.3). For example, very small pieces of aluminium confined in a shell
explode violently. If larger pieces of aluminium are used, the reaction is slower and
sparks are seen as pieces of burning metal being ejected.

FIGURE 7.1.3

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 171


Concentration
The concentration of solutes dissolved in a solution can influence the rate of their
reactions: higher concentrations usually lead to increased reaction rates.
Pollutants such as sulfur dioxide and nitrogen dioxide are released by cars and
many industrial processes. When these compounds react with rainwater, acids such
as sulfurous acid and nitric acid are formed. This causes the rainwater’s hydrogen
ion concentration to increase significantly and it is called acid rain. The increasing
acidity of rain over the past 200 years has caused many famous marble buildings
and statues to deteriorate much more rapidly due to the reaction between marble
and the acids (see Figure 7.1.4).
FIGURE 7.1.4 This limestone statue has
Pressure
(calcium carbonate) reacts more rapidly with In reactions involving gases, increasing the pressure on a reaction increases the rate
at which the reaction takes place. Increasing the pressure at constant temperature
will result (on average) in the reactant particles becoming closer together.
This will increase the chance of the gas molecules colliding, and therefore
increase the rate of reaction. Increasing the pressure of a reacting gas is the same as
increasing the concentration because you have the same mass in a smaller volume.
For this reason, engineers often employ high gas pressures in their design of
chemical processes that use gas-phase reactions. An example is the production of
ammonia gas by reacting hydrogen gas and nitrogen gas. Increasing the pressure
ensures a faster rate of reaction.

Temperature
As every cook knows, the temperature of an oven affects the rate of the chemical
reactions during baking. The higher the temperature, the more rapidly the reactions
occur.
FIGURE 7.1.5 Food is stored at low On the other hand, in hot weather it is wise to store fruit and vegetables in the
refrigerator so that the chemical reactions that cause them to over-ripen and then
spoil will be slowed down at the lower temperatures (Figure 7.1.5).

CHEMFILE
Fireworks and nanoparticles

FIGURE 7.1.6

172 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Catalysts
Some chemical reactions occur much more rapidly if another substance is added
to the reaction mixture. Such substances are called catalysts. Catalysts allow the
reaction to follow a more energetically favourable pathway.
For example, if you chew a piece of dry biscuit or bread for several minutes, you
may notice it tasting much sweeter. This happens because there is a catalyst present
in your saliva that speeds up the breakdown of starch into sweet-tasting sugars.
In the following sections, you will learn how each of these factors can cause
these changes in reaction rate.

MEASURING RATES OF REACTION EXPERIMENTALLY


The rate of reaction is defined as the change in concentration of a reactant or
product per unit time. The usual unit for a rate of reaction is M s–1.

To experimentally determine the rate of reaction, either directly or indirectly,


you need to measure how much of a reactant is being used up or how much of a
product is being formed in a given time period.
When a reaction involves gaseous products, this might involve measuring
changes in mass or gas volume with time.
The graphs shown in Figure 7.1.7 were obtained by measuring the mass of
carbon dioxide produced in the reaction between marble chips and hydrochloric
acid. The experiment was performed twice, first with large marble chips, then with
small marble chips.

CaCO3 + 2HCl → CaCl2 + CO2 + H2O


Volume of carbon dioxide

large pieces
of marble
(low surface area)

small marble
chips (high
surface area)

Time

FIGURE 7.1.7

The steeper initial gradient of the graph with small marble chips indicates that
the rate of production of carbon dioxide gas is faster with the marble chips that
have a higher surface area.
Colour changes and pH changes can also be used to follow the rate of some
reactions, depending on the colour and acidity of reactants and products.

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 173


7.1 Review
SUMMARY

• The rate of a reaction is the change in concentration • A range of experimental methods can be used to
of reactants or products over time. measure the rate of a reaction, including measuring
• The rate of a reaction may be increased by: the following during specific time intervals:
– increasing surface area – mass loss
– increasing the concentration of a reactant – volume of gas produced
in solution – colour change
– increasing the pressure of a gaseous reactant – concentration changes
– increasing temperature – pH change.
– adding a catalyst.

KEY QUESTIONS

1 Which one of the following changes would decrease the rate of the reaction
between zinc metal and dilute hydrochloric acid?
A Increasing the temperature of the hydrochloric acid
B Decreasing the size of the pieces of zinc
C Decreasing the concentration of the hydrochloric acid
D Decreasing the volume of hydrochloric acid used
2 Select the correct response in the statements about the five main ways
in which reaction rates can be increased.
a Increasing/decreasing surface area of solid reactants
b Increasing/decreasing the temperature of a reaction mixture
c Increasing/decreasing the concentration of a reactant in solution
d Increasing/decreasing the pressure of gaseous reactants
e Adding/removing a catalyst
3 The graph in Figure 7.1.8 shows the mass of carbon dioxide gas produced
during a 4-minute period of a reaction between marble chips (calcium
carbonate) and 1.0 M nitric acid.

5
Mass of CO2 evolved (g)

4
3
2
1
0
0 60 120 180 240
Time (s)

FIGURE 7.1.8

a Write a full chemical equation for this reaction.


b Explain whether the rate of this chemical reaction is increasing or
decreasing over time.
4 Describe one way of increasing the rate of each of the following reactions.
a Wood burning on a camp fire
b Removing excess mortar from between bricks using brick cleaner
c Baking a cake in the oven

174 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
7.2 Collision theory
The chemical equation for a reaction indicates the nature of the reactants and
products, but provides no information about the way in which the reaction proceeds.
Look at the equation for the decomposition of hydrogen peroxide:
2H2O2(l) → 2H2O(l) + O2(g)
This equation gives no indication about whether the reaction proceeds quickly
or slowly; nor can you tell how the products have been formed.
In fact, this reaction normally occurs very slowly, but when a catalyst, such as
crystals of potassium permanganate, are added to the hydrogen peroxide solution,
the reaction occurs rapidly, producing so much oxygen gas and heat that the reaction
mixture foams and that some of the liquid water vaporises (see Figure 7.2.1).
Chemical reactions occur as a result of collisions between the reacting particles.
This idea is part of the collision theory of reaction rates, which will be discussed
in this section.

COLLISION THEORY AND ACTIVATION ENERGY


During chemical reactions, particles (atoms, molecules or ions) collide and are
rearranged to produce new particles. Consider the decomposition reaction of
hydrogen peroxide:
2H2O2(l) → 2H2O(l) + O2(g)
The collision that forms the first step of the reaction occurs between the two
hydrogen peroxide molecules. If this collision is to result in the formation of
molecules of water and oxygen, the collision must occur in such a way that the
covalent bonds in the hydrogen peroxide break. To break bonds, energy is required.
The collision theory of reactions explains why some collisions result in reactions
and others do not. According to collision theory, for a reaction to occur, the reactant
particles must:
• collide with each other
• collide with sufficient energy to break the bonds within the reactants
• collide with the correct orientation to break the bonds within the reactants and
so allow the formation of new products.
If a collision does not meet all of these requirements, then no reaction occurs.
FIGURE 7.2.1
In  fact, most collisions do not result in a chemical reaction. Collision theory
peroxide is usually very slow, but the addition
explains why this is the case.

Activation energy
For a reaction to occur between reactant molecules, the molecules must collide with
a certain minimum amount of energy. Unless this minimum amount of energy is
met or exceeded, the colliding molecules will rebound and simply move away from
each other without reacting.
The minimum energy that a collision must possess for a reaction to occur
is called the activation energy, Ea. (You learned about activation energy in
Chapter 2.) When the energy of a collision is equal to or greater than the activation
energy, a reaction can occur.
Activation energy can be represented on an energy profile diagram. Energy
profile diagrams for both endothermic and exothermic reactions were looked at
in Chapter 2, page 44. An energy profile diagram represents the potential energies
of the reactants and the products over the course of the reaction.
Energy profile diagrams for both exothermic and endothermic reactions have
a peak that represents the activation energy. This is sometimes referred to as
the activation energy barrier, and represents the minimum energy that must be
absorbed in order to break the bonds of reactants so that a chemical reaction can
progress. The activation energy is measured from the energy of the reactants to the
top of the peak.

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 175


You will recall that an exothermic reaction releases more heat energy during the
reaction than it absorbs. An endothermic reaction absorbs more heat energy during
the reaction than it releases. This is represented on the diagram as ∆H and is the
difference in energy between the reactants and the products.

Transition state
When the activation energy is absorbed, a new arrangement of the atoms known as
the transition state occurs. The transition state occurs at the stage of maximum
potential energy in the reaction: the activation energy (see Figure 7.2.2). Bond
breaking and bond forming are both occurring at this stage, and the arrangement
of atoms is unstable. The atoms in the transition state rearrange into the products
as the reaction progresses.

transition state

Potential energy

I2 activation
2HI
energy, Ea
H2 products
ΔH
reactants
Reaction progress

FIGURE 7.2.2 2
(g) + I2(g) →

Activation energy and reaction rate


The size of the activation energy determines how easy it is for a reaction to occur
and therefore what proportion of collisions results in a successful reaction. For this
reason, the reaction rate is dependent upon the activation energy.
The existence of an activation energy for a reaction means that collisions
between reactants do not always result in a chemical change. For example, nitrogen
(N2) and oxygen (O2) molecules collide frequently in the air around us at room
temperature. However, it is only when energy is provided by a spark, such as in car
engines or during a lightning strike, that the energy of the collisions is increased
enough to overcome the activation energy barrier. This allows nitrogen monoxide
to be produced. The nitrogen monoxide formed in this process can then react to
form brown nitrogen dioxide (NO2), a poisonous gas that is a major contributor to
the formation of the photochemical smog seen in Figure 7.2.3.

FIGURE 7.2.3
2

176 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Orientation of colliding molecules
For a reaction to occur, reactants need to collide with enough energy to provide
the activation energy. Reacting molecules must also collide with each other in the
correct orientation in such a way that particular bonds in the reactants are broken
and new bonds are formed in the products.
Figure 7.2.4 shows the importance of collision orientation. In the decomposition
of hydrogen iodide gas into hydrogen gas and iodine gas, two hydrogen iodide
molecules must collide with hydrogen and iodine atoms orientated towards each
other, for a reaction to possibly occur. If the collision orientation is incorrect, the
particles simply bounce off each other, and no reaction occurs.

HI HI

HI HI

Unfavourable orientation Favourable orientation


Reaction is unlikely. Reaction is likely.
2HI(g) → H2(g) + I2(g)

FIGURE 7.2.4

CHEMFILE
A little too reactive!

small activation energy, Ea


C3H5(NO3)3
Hr
equation:
H O →
Energy

3 5 3 9

CO2, H2O, N2, O2


Hp

Reaction progress
FIGURE 7.2.5 Nitroglycerin has a very low activation

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 177


7.2 Review
SUMMARY

• The activation energy of a reaction is the minimum • Collision theory is a theoretical model that accounts
amount of energy required to break reactant bonds for the rates of chemical reactions in terms of
to allow a reaction to proceed. It is the minimum collisions between particles during a chemical
amount of energy that a collision between reactant reaction.
particles must possess for a reaction to occur. • According to collision theory, for a reaction to occur,
• The transition state is an arrangement of atoms the reactant particles must:
that occurs when the activation energy is absorbed. – collide with each other
The transition state is an unstable state in which – collide with sufficient energy to break the bonds
bonds in the reactants are being broken and bonds within the reactants
in the products are starting to form. – collide with the correct orientation to break the
• An energy profile diagram shows the activation bonds within the reactants and so allow the
energy as a peak of highest potential energy formation of new products.
between the energy of the reactants and the energy
of the products.

KEY QUESTIONS

1 According to the collision theory, which one of the following is not essential
for a reaction to occur?
A Molecules must collide to react.
B The reactant particles should collide with the correct orientation.
C The reactant particles should collide with enough energy to overcome
the activation energy barrier.
D The reactant particles should collide with double the energy of the
activation energy.
2 Which one of the following is the energy required to produce the transition
state in a reaction?
A Activation energy
B Difference in energy between the products and reactants
C Difference in energy between the products and the activation energy
D Transition state energy
3 When 1 mol of methane gas burns completely in oxygen, the process of
bond breaking uses 3380 kJ of energy and 4270 kJ of energy is released
as new bonds form.
a Write a balanced chemical equation for the reaction.
b Calculate the value of the heat of reaction, ∆H, for the reaction.
c Draw and label a diagram to show the changes in energy during the
course of the reaction.
4 The formation of hydrogen iodide from its elements is represented by
the equation:
H2(g) + I2(g) → 2HI(g)
This reaction has an activation energy of 167 kJ mol–1 and the heat of
reaction, ∆H, is +28 kJ mol–1. What is the activation energy for the reverse
reaction, the decomposition of 2 mol of hydrogen iodide?

178 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
7.3 Effect of temperature on rate
of reaction
Earlier in this chapter you saw that the rate of a reaction can be changed by the:
• surface area of a solid reactant
• concentration of reactants in a solution
• pressure of any gaseous reactants
• temperature of the reaction
• presence of a catalyst.
In any given reaction mixture, only a certain proportion of the collisions are
successful. To increase a reaction rate, you can increase the proportion of successful
collisions by:
• increasing the frequency of successful collisions by increasing the number of
collisions that can occur in a given time
• increasing the proportion of collisions that have energy that is equal to or greater
than the activation energy (i.e. overcome the activation energy barrier).
In this section, you will consider how various changes to conditions can affect
the proportion of successful collisions that occur between reactant particles and
hence change the rate of reaction.

INCREASING THE FREQUENCY OF COLLISIONS


The rate of a reaction increases as the frequency of collisions increases. The
frequency of collisions between reactants can be increased by:
• increasing the concentration of the reactants. Collisions occur more frequently
when particles are closer together
• increasing the surface area of a solid reactant.

Changing concentration or pressure


In section 7.1, you learned that the rate of a reaction can be increased by increasing
the concentration of a reacting solution or the pressure of a reacting gas. This can
be explained by collision theory.
The rate of a reaction increases when the frequency of collisions between
reactants increases. When the concentration of a solution increases, there
are more reactant particles moving randomly in a given volume of solution
(see Figure 7.3.1). The frequency of collisions consequently increases and so more
successful collisions occur in a given time.

10× increase in
concentration of
one of the
reactants

FIGURE 7.3.1

For a reaction in the gas phase, the pressure of the gases can be increased either
by adding more gas to a fixed volume container or by decreasing the volume of a
container with a variable volume, such as a gas syringe. Increasing the pressure
increases the concentration of gas molecules, causing more frequent collisions and
increasing the number of successful collisions in a given time.

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 179


Changing surface area
When a solid is involved in a reaction, only the particles at the surface of the solid
are involved in the reaction. The number of particles at the surface depends on the
surface area of the substance. As you can see in Figure 7.3.2, breaking a solid into
smaller parts means that more particles are present at the surface and available to
react. The surface area has increased.
As a consequence of the greater number of exposed particles, the frequency of
collisions between these particles and the other reactant particles increases, and so
the reaction occurs more rapidly.

zinc Cl– Cl–

H+

H+
zinc

granules Granules of zinc metal powdered Zn Zinc powder with large surface
of Zn react slowly with HCl. area reacts rapidly with HCl.

FIGURE 7.3.2
+
3
ion is represented as H+

The effect of increasing surface area can be seen when setting up an open fire
at home or on a camp. It is best to first light a pile of kindling rather than trying to
to explain the effect of directly light large logs. The kindling has a larger surface area than the logs, so it
concentration, pressure and catches fire more easily and will then burn rapidly, providing enough sustained heat
surface area on the rate of a energy to make the logs catch fire as well.
discuss the effect on either collision Worked example 7.3.1
USING COLLISION THEORY TO EXPLAIN CHANGES IN RATES OF REACTIONS

There have been many explosions in underground coal mines due to the
presence of coal dust. Explain this observation in terms of collision theory.

Thinking Working

Consider the state of the reactants. Coal is a solid. In the mine, there would
be lumps of coal and also powdered
coal.

Relate the state of the reactant to The surface area of powdered coal is
the factor that affects the reaction greater than that of solid coal. When the
rate and explain in terms of collision surface area increases, the frequency of
theory. collisions increases and so the rate of
reaction increases.

Return to the question to complete An explosion is a very fast reaction.


your answer. The very large surface area of the
coal dust allows for an increase in the
frequency of collisions with reacting
particles, which increases the reaction
rate so much that explosions occur.

180 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Worked example: Try yourself 7.3.1
USING COLLISION THEORY TO EXPLAIN CHANGES IN RATES OF REACTIONS

Iron anchors recovered from shipwrecks at considerable depths can show little
corrosion after years in the sea, whereas anchors recovered from shallow water
are badly corroded. Explain this observation in terms of collision theory.

INCREASING THE ENERGY OF COLLISIONS


As you have seen, a reaction can be made to occur more rapidly by increasing the
concentration of the reactants or, for solids, increasing the surface area. A change
in temperature can also have a major effect on the rate of a reaction. An increase
in temperature not only increases the frequency of collisions, it also increases the
kinetic energy of the particles and hence the energy of their collisions.

Maxwell–Boltzmann distribution
At any particular temperature, the particles in a substance have a range of kinetic
energies. Although most of the particles have similar kinetic energies, there are always
some particles with a high energy or a low energy. This range of energies is shown
on a graph called a Maxwell–Boltzmann distribution curve, also known as a
kinetic energy distribution diagram. Figure 7.3.3 shows how the distribution of
energies is represented in a Maxwell–Boltzmann distribution curve.
with kinetic energy, E
Number of particles

Kinetic energy (E)

FIGURE 7.3.3

During a reaction at a given temperature, only a small proportion of the reactant


particles have kinetic energy that is equal to or greater than the activation energy
and so are able to react. You can see this in Figure 7.3.4 as a small shaded area to
the right of the activation energy, Ea.
Number of particles

Particles do not have


enough energy to
cause a reaction.
Activation energy, Ea

Particles have enough


energy to react.
Particle kinetic energy

FIGURE 7.3.4

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 181


The relationship between kinetic energy and velocity is given by the formula
1
KE = mv2. As the temperature of a reaction system increases, the average kinetic
2
energy of the particles increases and the average speed of the particles in the system
increases as well.
This is illustrated in Figure 7.3.5 in which the range of kinetic energies for a
gas at three different temperatures is shown. Note that the area under the curve,
which is equal to the total number of particles in the sample, stays constant when
the temperature is changed. As the temperature increases, the increasing average
kinetic energy of the particles can be seen by the movement to the right of the peak
in the Maxwell–Boltzmann curve.

0°C
Number of molecules

1000°C

CHEMFILE
2000°C
Ötzi the Iceman

Kinetic energy

FIGURE 7.3.5

As the temperature of a reaction increases, the increased speed of particles


causes more collisions, increasing the frequency of successful collisions and the
rate of reaction.
The increased kinetic energy of the particles also means that collisions occurring
at higher temperatures have greater energy than those at lower temperatures. More
particles will have energies that are greater than or equal to the activation energy
and so the proportion of successful collisions also increases.
When the temperature increases, the increase in reaction rate due to the
increased energy of the collisions significantly outweighs the increase in reaction
rate due to the increased frequency of collisions.
A temperature increase of just 10°C causes the rate of many reactions to double
(an increase of 100%), but it can be shown that this is not due to the increased
frequency of collisions. The frequency of collisions only increases by about 3%
when the temperature increases by 10°C. The main reason why the reaction rate
increases is that more particles have sufficient energy to overcome the activation
energy barrier of the reaction.
FIGURE 7.3.6 Ötzi the Iceman was so well

182 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
7.3 Review
SUMMARY

• Collision theory can be used to explain the increase • Increase in temperature results in an increase in the:
in rate of reaction by an increase in: – frequency of collisions between reactants
– concentration of a reactant solution – number of successful collisions in a given time
– pressure of a gaseous reactant – most importantly, energy of collisions, so an
– surface area of a solid reactant increased proportion of collisions has an energy
– temperature. larger than the activation energy for the reaction.
• Increase in concentration, pressure or surface area
results in an increase in the:
– frequency of collisions between reactants
– number of successful collisions in a given time.

KEY QUESTIONS

1 Which one of the following alternatives correctly explains why a sample


of magnesium reacts more rapidly with 1 M HCl than with 0.1 M HCl?
A The energy of collisions between reactant particles is greater for the
reaction containing 1 M HCl.
B The rate of collisions between reactant particles is greater for the reaction
containing 0.1 M HCl.
C There are more collisions between the magnesium and 1 M hydrochloric
acid.
D The frequency of collisions between reactant particles is greater than for
the reaction containing 1 M HCl.
2 Which one or more of the following may be true if a reaction is observed to
proceed very slowly?
A The activation energy may be very large.
B The temperature may be low.
C Few collisions may be occurring with the correct orientation.
3 A number of experiments involving the reaction between 100 mL of
hydrochloric acid and 5 g of calcium carbonate were carried out. Rearrange
experiments A–F to place them in increasing order of rate of reaction (slowest
to fastest).
A Powdered CaCO3 and 1 M HCl are mixed at 40°C.
B Small pieces of CaCO3 and 1 M HCl are mixed at 15°C.
C Powdered CaCO3 and 1 M HCl are mixed at 25°C.
D Large pieces of CaCO3 and 0.5 M HCl are mixed at 15°C.
E Powdered CaCO3 and 1 M HCl are mixed at 15°C.
F Small pieces of CaCO3 and 0.5 M HCl are mixed at 15°C.
4 Account for the following observations with reference to the collision model of
particle behaviour.
a Surfboard manufacturers find that fibreglass plastics set within hours in
summer but may remain tacky for days in winter.
b A bottle of fine aluminium powder has a caution sticker warning ‘Highly
flammable, dust explosion possible’.
c A potato cooks much more slowly in a pot of boiling water on a trekking
holiday in Nepal than a potato boiled in a similar way in the Australian bush.

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 183


7.4 Catalysts
In this section, you will learn how catalysts increase the rate of reaction.
The change in reaction rate when a catalyst is present is often very substantial.
The action of a catalyst can be understood using collision theory and the changes
in energy that occur during a chemical reaction. Catalysts play an important role
in industrial chemistry, in limiting air pollution and  in controlling biochemical
processes, as shown in the examples in Figure 7.4.1.

(a) (b)

FIGURE 7.4.1

CATALYSTS AND ACTIVATION ENERGY


Energy absorbed You have already learned that the potential energy changes associated with a reaction
as bonds in can be represented as an energy profile diagram of the reaction. An energy profile
reactants break transition state
diagram for an exothermic reaction is shown in Figure 7.4.2.
activation The activation energy is the minimum amount of energy required for a reaction
energy, Ea to take place. On the energy profile diagram, the activation energy is measured
Energy

reactants from the energy of the reactants to the peak of the energy profile diagram.
The enthalpy change, ∆H, can also be represented on an energy profile diagram
Energy released ΔH
as bonds form
and is equal to the difference in energy between the products and the reactants.
in products
products
Some reactions occur very readily because they have very small activation
energies, Ea. These reactions need only a small amount of energy to be absorbed
Reaction progress for bonds in the reactants to be broken.
FIGURE 7.4.2 Many reactions occur much more rapidly in the presence of a particular element
or compound. These substances are known as catalysts. Catalysts are not consumed
during the reactions they speed up, and so do not appear as either reactants or
products in reaction equations.
Catalysts are able to cause a reaction to occur more quickly because they
provide a new reaction pathway, which causes the activation energy barrier of the
overall reaction to be dramatically reduced, as seen in the energy profile diagram
in Figure 7.4.3.

184 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
uncatalysed
Ea reaction
without pathway
Potential energy
catalyst
catalysed
Ea reaction
with pathway
catalyst
reactants

products

Reaction progress

FIGURE 7.4.3

With the catalyst present and a lower activation energy, the colliding particles
are more likely to have energies that exceed this lower barrier, causing the bonds
in the reactants to be broken more frequently. As a result, a greater proportion of
collisions are ‘successful’; that is, they lead to the formation of products. Thus, the H for
reaction rate is increased.
The Maxwell–Boltzmann curve in Figure 7.4.4 shows the smaller number of
particles with energies that exceed the activation energy in an uncatalysed reaction
(shaded in red) compared with the number of particles with energies that exceed
the activation energy in a catalysed reaction (regions shaded in red and blue).

catalysed
Number of collisions
with a given energy

activation
energy

uncatalysed
activation
energy

This increases the proportion of

Eʹa Ea
Kinetic energy
the proportion of successful
FIGURE 7.4.4 A catalyst provides a reaction pathway with a lower activation energy, increasing the

CHEMFILE
MOUNT

Routes from Melbourne KO


S C IU S Z K O
to Canberra

THE

FOO
T H IL L S

Melbourne Canberra

FIGURE 7.4.5

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 185


TYPES OF CATALYSTS
Depending on the physical state of the chemicals involved in the reaction and the
catalyst, catalysts can be divided into two groups.
• Homogeneous catalysts are in the same physical state as the reactants and
products of the reaction.
• Heterogeneous catalysts are in a different physical state from the reactants
and products of the reaction.
An example of homogeneous catalysis occurs in the upper atmosphere and
has contributed to the depletion of the ozone layer. Chlorine atoms in the gaseous
state act as catalysts in the decomposition of ozone gas into oxygen gas. The
chlorine atoms may have come from chlorofluorocarbons (CFCs) released into the
atmosphere from refrigerators or air conditioners.
You may be familiar with the catalysed decomposition of a hydrogen peroxide
solution using the black powder manganese(IV) oxide (MnO2). This is an example
of the use of a heterogeneous catalyst.

CATALYSTS IN INDUSTRY
The chemical industry uses catalysts extensively. Chemists prefer to use
heterogeneous catalysts for industrial processes because they are:
• more easily separated from the products of a reaction
• much easier to reuse
• able to be used at high temperatures.
Particles at the surface of some solids of high surface area tend to adsorb (form
a bond with) gas molecules that strike the surface. Adsorption distorts bonds in
the gas molecules or may even break them completely. This allows a reaction to
proceed more easily than it would if the solid were absent.
These solid surfaces provide a new way for the reaction to occur (a new reaction
pathway) that has a significantly lower activation energy.
A powdered or sponge-like form of a solid catalyst is often used to provide the
greatest possible surface area. With a larger surface area, more reactant molecules
can be adsorbed and the reaction is even faster.

EXTENSION

Heterogeneous catalysis and the Haber process


The Haber process is a very important commercial Hydrogen and nitrogen molecules both adsorb onto the
reaction that produces ammonia gas, which is used iron surface (see Figure 7.4.6a). As they attach themselves
to make fertilisers, nylon, explosives and some to the surface, the covalent bonds within their molecules
pharmaceuticals. In the Haber process, hydrogen and break (Figure 7.4.6b).
nitrogen gas are converted to ammonia (NH3), using a The hydrogen and nitrogen atoms now readily combine
catalyst of powdered iron. to form ammonia molecules and move away from the iron
The reaction is represented by the equation: surface (Figure 7.4.6c). The catalyst remains unaltered by
N2(g) + 3H2(g) → 2NH3(g) ∆H = –91 kJ mol–1 the reaction.

186 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
(a) (b) (c)
hydrogen
nitrogen molecules
molecule

Molecules are adsorbed on


the catalyst and bonds break.

iron catalyst surface

New bonds form to


FIGURE 7.4.6 make ammonia molecules.

Without a catalyst, temperatures over 3000°C are ‘barrier’—the energy needed to break the covalent bonds
needed for a significant reaction to occur. The catalyst in the nitrogen and hydrogen molecules. Even though
allows the manufacture of ammonia to proceed at an collisions are less frequent at 500°C than at 3000°C, a
economical rate using a temperature of about 500°C. greater proportion of colliding particles have sufficient
The iron catalyst provides an alternative reaction energy to successfully react.
pathway that dramatically reduces the activation energy

CHEMFILE
Catalytic converters in cars

H →


catalyst coated
on a metal
framework

catalyst
carbon dioxide,
water and
nitrogen
exhaust gases: unburnt
fuel, nitrogen oxides,
carbon monoxide
and air
FIGURE 7.4.7

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 187


7.4 Review
SUMMARY

• The rate of a reaction can be increased by using


a catalyst.
• A catalyst provides an alternative reaction pathway uncatalysed reaction
that has a lower activation energy. catalysed reaction
• Energy profile diagrams (see Figure 7.4.8), which Ea

Energy
can include catalysed and uncatalysed pathways, Eʹa
Eʹa < Ea
may be used to represent the enthalpy changes Hr
and activation energy associated with a chemical
reaction. Hp
• A catalyst provides a new reaction pathway and it is
not used up in the reaction.
• When a catalyst is present, a greater proportion of
Reaction progress
the collisions between particles exceed the activation
energy barrier of the reaction and therefore lead to a FIGURE 7.4.8
chemical change.

KEY QUESTIONS

1 Consider the reaction between solutions V and W that produces X and Z


according to the equation:
V(aq) + W(aq) → X(aq) + Z(aq)
The energy profile diagram for this process is shown in Figure 7.4.9.
Which one of the following alternatives describes the change that a catalyst
produces to increase the reaction rate? A
A B only is decreased. V+W
B A only is decreased. C
Energy

C A, B and C are decreased. B


D A and C only are decreased.
X+Z
2 Explain the meaning of:
a catalyst
b activation energy.
Reaction progress
3 If a sugar cube is held in the flame of a candle, the sugar melts and browns
FIGURE 7.4.9
but does not burn. However, the cube burns if salt is first rubbed into it,
even though the salt does not react. Explain the effect of the salt on the
activation energy of this combustion reaction.
4 a Explain why surface properties are important to the operation of catalysts.
b Many industrial catalysts are made into porous pellets. What is the reason
for this?

188 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Chapter review
KEY TERMS

acid rain energy profile diagram Maxwell–Boltzmann


activation energy exothermic distribution curve
adsorption heterogeneous catalyst photochemical smog
catalysis homogeneous catalyst rate of reaction
catalyst kinetic energy reaction pathway
collision theory kinetic energy distribution surface area
endothermic diagram transition state

Investigating the rate of chemical reactions


1 Which one of the following is the correct definition of
rate of reaction?
A The time it takes for all of a reactant to be used up

Mass of mixture (g)


B How fast a reaction is going at the end of 1 minute
C How much a reaction is bubbling
D The change in concentration of reactants or
products over time
2 Which of the following combinations of reactants will
produce the greatest initial reaction rate?
2HCl(aq) + CaCO3(s) → CaCl2(aq) + H2O(l) + CO2(g)
A CaCO3 chips and 1 M HCl
B CaCO3 chips and 2 M HCl
Time (s)
C CaCO3 powder and 2 M HCl
FIGURE 7.5.1
D CaCO3 powder and 1 M HCl
3 The following changes are made to a reaction mixture. a Explain why the mass of the mixture initially
Which change will lead to a decrease in reaction rate? decreases with increasing time.
A Smaller solid particles are used. b Based on the information provided, determine
B The temperature is decreased. which reactant is limiting.
C A catalyst is added. c Redraw Figure 7.5.1, then sketch in the expected
D The concentration of an aqueous reactant curve if 500 mL of 1.00 M nitric acid had
is increased. been used instead. Label your new graph line.
4 Which of the following is the correct unit for Explain the difference in shape.
measuring the rate of a reaction? d Redraw Figure 7.5.1, then sketch in the expected
A mol–1 L s–1 curve if 5.00 g of powdered copper was used
B mol L–1 s–1 instead. Label this new graph line. Explain the
C mol–1 L–1 s difference in shape.
D mol L s–1 Collision theory
5 A 5.00 g piece of copper was dissolved in a beaker 6 According to collision theory, what must happen for
containing 500 mL of 2.00 M nitric acid. The equation a reaction to occur?
for the reaction that occurred is:
3Cu(s) + 8HNO3(aq) →
3Cu(NO3)2(aq) + 2NO(g) + 4H2O(l)
The changing mass of the mixture was observed for
a period of time, and the graph in Figure 7.5.1 was
obtained.

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 189


7 Figure 7.5.2 shows the substitution reaction between b Explain what is meant by the term ‘activation
chloromethane and a hydroxide ion. energy’.
Using collision theory, explain why collision 1 might be c Is the reaction endothermic or exothermic?
successful while collisions 2–4 will not be successful. d Label the transition state in this reaction on your
diagram.
e What bonds are beginning to be broken and formed
to produce the transition state?
9 Hydrogen reacts explosively with oxygen to form water.
a What chemical bonds are broken in the reaction?
b What chemical bonds are formed?
c Explain how the energy changes during bond-
breaking and bond-forming affect the overall energy
change for the reaction.
collision 1 collision 2 d Why is there no reaction until the reaction mixture
is ignited?

Effect of temperature on rate of reaction


10 Which one of the following alternatives correctly
explains why the rate of reaction between 1 M CuSO4
and powdered zinc is greater than with an equal
amount of large zinc pieces.
A The energy of collisions between the Cu2+(aq) ions
and powdered zinc is greater than with the large
collision 3 collision 4 zinc pieces.
B The frequency of collisions between the Cu2+(aq)
FIGURE 7.5.2 Possible collision orientations in the substitution
ions and powdered zinc is greater than with the
large zinc pieces.
8 Figure 7.5.3 is an energy profile diagram for the C The energy of collisions between the Cu2+(aq)
substitution reaction between chloromethane and ions and large zinc pieces is greater than with the
hydroxide ion. powdered zinc.
D The frequency of collisions between the Cu2+(aq)
ions and large zinc pieces is greater than with the
– powdered zinc.
H
11 Which one of the following statements correctly
Cl C OH describes what must occur when reactant particles
collide and react?
H H A Colliding particles must have an equal amount of
H kinetic energy.
B Colliding particles must have different amounts of
H C Cl + OH–
kinetic energy.
Energy

H C Colliding particles must have kinetic energy equal


to or greater than the average kinetic energy.
D Colliding particles must have kinetic energy
H equal to or greater than the activation energy of
the reaction.
H C OH + Cl–
12 Account for the following observations with reference
H to the collision model of particle behaviour.
a Refrigeration slows down the browning of sliced
apples.
Reaction progress
b Hydrogen gas burns in air to produce water vapour.
FIGURE 7.5.3
Using pure oxygen gas instead of air increases the
rate of this reaction.
a Copy this diagram and label ∆H and activation
energy.

190 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
Catalysts a What is the magnitude of the activation energy of
13 Which one of the following factors would not increase this reaction?
the rate of decomposition of hydrogen peroxide? b What is ∆H for this reaction?
2H2O2(aq) → 2H2O(l) + O2(g) Several groups of scientists have claimed to have split
A Increasing the pressure of oxygen gas water into hydrogen and oxygen using a molybdenum
B Increasing the concentration of hydrogen peroxide catalyst:
C Increasing the temperature of hydrogen peroxide 2H2O(g) Mo 2H2(g) + O2(g)
D Adding a potassium iodide catalyst c Sketch energy change graphs for this reaction with
and without the presence of a catalyst.
14 Which statement is correct for the effects of catalyst
d What is the value of ∆H for this water-splitting
and concentration on the rate of reaction?
equation?
Adding a catalyst Increasing the concentration
Connecting the main ideas
A Collision frequency Collision frequency increases
18 a Figure 7.5.5 shows the distribution of energies
increases
of particles in a substance at two different
B Activation energy Activation energy decreases temperatures, 40°C and 60°C. Indicate the
decreases temperatures represented by graphs A and B.
C Activation energy Collision frequency increases
A
decreases

Number of particles
B
D Collision frequency Activation energy decreases
increases
15 a What are the five factors that influence the rate of
a reaction?
b Classify the five factors from part a according to Kinetic energy
whether they increase the proportion of successful
FIGURE 7.5.5
collisions by:
i increasing collision frequency b Copy this diagram for temperature B and use
ii increasing the proportion of collisions that have the diagram to show the effect of a catalyst on
energy equal to or greater than the activation a reaction.
energy. c Use the diagram you have drawn in part b to
16 The Haber process involves the reaction of nitrogen explain in terms of collision theory how a catalyst
gas and hydrogen gas to make ammonia gas. increases the rate of a reaction.
Describe two ways the rate of this reaction could be 19 Lumps of limestone, calcium carbonate, react readily
increased, at constant temperature. Using collision with dilute hydrochloric acid. Four large lumps of
theory, explain why rate is increased. limestone, mass 10.0 g, were reacted with 100 mL
17 Many major car makers have plans for hydrogen- 0.100 M acid.
powered cars. In the fuel cells of these cars, hydrogen a Write a balanced equation to describe the reaction.
reacts with oxygen from the air to produce water. b Which reactant is in excess? Use a calculation to
2H2(g) + O2(g) → 2H2O(g) support your answer.
Energy changes for the reaction are shown in the c Describe a technique that you could use in a school
graph in Figure 7.5.4. laboratory to measure the rate of the reaction.
d 10.0 g of small lumps of limestone will react at a
1370 different rate from four large lumps. Will the rate of
reaction with the smaller lumps be faster or slower?
Explain your answer in terms of collision theory.
Energy (kJ mol–1)

e List two other ways in which the rate of this reaction


can be altered. Explain your answer in terms of
collision theory.
0
2H2(g)
_572 + O2(g)
2H2O(g)

FIGURE 7.5.4

CHAPTER 7 | RATE OF CHEMICAL REACTIONS 191


20 Figure 7.5.6 shows the energy profile diagram for the
Any spark or fire will set off an explosion of
reaction of hydrogen and iodine to form hydrogen
hydrogen gas, and that is what happened on the
iodide:
H2(g) + I2(s) 2HI(g) MV B. Onal.

a What is the main reason the new reduction process


uses less energy than the old process?
b Write equations showing the oxidation of iron by
Energy

oxygen to form iron(II) oxide and iron(III) oxide.


c If water is present the oxidation reaction speeds up
100-fold. Is water acting as a catalyst? Explain your
answer.
Time d Is the reaction shown in equation 3 endothermic
FIGURE 7.5.6 or exothermic?
e List the factors that increased the rate of reaction
in equation 3.
a Copy the diagram and label the following: H2(g) and f Firefighters were not able to use water to put out
I2(s); HI(g); ∆H; activation energy. the fire in the cargo hold. Why not? Suggest how
b Is the reaction endothermic or exothermic? they could put out the fire.
c On the diagram draw the energy profile that would 22 Chemical reactions in the body normally take place at
result if a catalyst was used in the reaction. 37°C. Explain how the rate of chemical reactions in the
21 Read the article and answer the questions that follow. body can account for the following facts.
a The body often responds to illness by an increase
Exploding iron in temperature, accompanied by a higher pulse rate
In 1996, while the Turkish ship MV B. Onal was riding and faster breathing.
at anchor in Delaware Bay, near Philadelphia in the b People rescued from drowning after 20–30 minutes
USA, a 2-tonne hatch cover suddenly blew off. As the in freezing water can sometimes survive and
ship was carrying a cargo of iron, the surprised crew recover with no brain damage.
asked themselves, ‘Can iron explode?’ 23 The first step in most toffee recipes is to dissolve
As you may be aware, traditionally iron oxide about 3 cups of sugar in 1 cup of water. Although
(Fe2O3) is reduced to molten iron in a blast furnace sugar is quite soluble in water, this step could be time-
A new process that uses less energy has been consuming. Use your knowledge of reaction rates to
developed. Iron oxide is converted directly to solid iron suggest at least three things you could do to increase
without having to heat the reactants to the melting point the rate of dissolution without ruining the toffee.
of iron. Iron oxide is heated to 550°C in the presence
of carbon monoxide and hydrogen gas. The iron oxide
is reduced to iron by both gases with the formation of
carbon dioxide or water.
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) (1)
Fe2O3(s) + 3H2(g) → 2Fe(s) + 3H2O (g) (2)
The pellets of pure iron that are formed are
extremely porous and full of many tiny holes, in
contrast to the solid formed when the molten iron from
a blast furnace cools. Under the right conditions the
iron pellets can be oxidised back to iron oxide.
In most cases, iron is oxidised slowly by oxygen
back to iron oxide and the resulting heat can readily
escape. If the pellets are more than 1 metre deep, as
in the hold of a ship, the heat cannot escape quickly
enough and the temperature rises. This speeds up the
reaction rate. If the temperature increases sufficiently
and water is present, another reaction occurs and the
oxidation rate is speeded up 100-fold, with the release
of more heat:
Fe(s) + H2O(g) → FeO(s) + H2(g) (3)

192 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
CHAPTER

Extent of chemical reactions

In this chapter, you will investigate the ideas of reversibility and irreversibility of
chemical systems. This study of reversible reactions will introduce the concept
of chemical equilibrium.
Various factors can change the position of a chemical equilibrium. Le Châtelier’s
principle enables us to understand the effects of changes in concentrations in
solutions, pressures of gases and temperature on an equilibrium.
The fact that many reactions do not proceed to completion has serious
consequences on the efficiency of chemical manufacturing industries. You will
learn how the reaction conditions chosen for an industrial process can be adjusted
to ensure optimum efficiency, taking into account considerations of rate and
equilibrium yield.
You will also learn how to write a mathematical relationship, known as an
equilibrium law, for an equilibrium system. This law can be used to calculate
the relative amounts of reactants and products present when a reaction is
at equilibrium.

Key knowledge
• The distinction between reversible and irreversible reactions, and between rate
and extent of a reaction
• Homogenous equilibria involving aqueous solutions or gases with reference to
collision theory and representation by balanced chemical or thermochemical
equations (including states) and by concentration–time graphs
• Calculations involving equilibrium expressions and equilibrium constants
(Kc only) for a closed homogeneous equilibrium system including dependence
of value of equilibrium constant, and its units, on the equation used to
represent the reaction and on the temperature
• Le Châtelier’s principle: identification of factors that favour the yield of a
chemical reaction, representation of equilibrium system changes using
concentration–time graphs and applications, including competing equilibria
involved in the occurrence and treatment of carbon monoxide poisoning
resulting from incomplete combustion of fuels

VCE Chemistry Study Design extracts © VCAA (2015); reproduced by permission.


8.1 Dynamic equilibrium
In this section, you will learn that some reactions can occur in both the forward and
reverse directions. These reactions are called ‘reversible reactions’.
Reversible chemical systems are encountered in many everyday situations,
including chemical manufacturing processes, the reactions of ions within individual
cells in your body and the reactions carbon dioxide undergoes in the environment.
This section also describes how some reversible reactions can reach a point
where they appear to ‘stop’. At this point, the concentrations of the reactants and
products remain constant, even though there are still reactants remaining.
The fact that many reactions do not proceed to completion has serious
consequences for the production of chemicals by industry. The presence of large
amounts of unreacted starting materials in reaction mixtures is wasteful and costly.
The profitability of an industry depends on the yield—the extent of conversion of
reactants into products.
Although these reactions appear to stop, they actually continue to proceed. If
you could see what was occurring at the atomic scale, you would notice that as
rapidly as the reactants are forming products, the products are re-forming reactants.
This  situation can be likened to the queue shown in Figure 8.1.1. Although the
length of the queue may seem constant, people at the front are continually leaving
the queue and others are joining it at the back at the same rate.

FIGURE 8.1.1 A queue of constant length can be likened to a reaction that appears to have stopped,

194 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
OPEN AND CLOSED SYSTEMS
In previous chapters, you learned that a chemical reaction can be regarded surroundings surroundings
as a system, with everything else around it (the rest of the universe) being the
surroundings. In an endothermic reaction, the system absorbs energy from energy energy
the surroundings, whereas in an exothermic reaction, energy is released to
system system
the surroundings.
Figure 8.1.2 illustrates how you can distinguish between two different types matter
of systems:
• open systems Open system Closed system
• closed systems. FIGURE 8.1.2 Open systems exchange
The most common situation in everyday life is an open system. In an open
system, matter and energy can be exchanged with the surroundings. In contrast, a Closed systems only exchange energy with
closed system only exchanges energy with the surroundings.
Some everyday examples of open and closed systems are illustrated in
Figure 8.1.3.

(a)

(b)
In a closed system, only
energy can be exchanged

FIGURE 8.1.3

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 195


IRREVERSIBLE AND REVERSIBLE SYSTEMS
You may have thought, as a younger student, that when chemical reactions occur,
the reactants form products and these products cannot be converted back to
the reactants. Such reactions, which occur only in one direction, are called non-
reversible or irreversible reactions.
Baking a cake, like the one shown in Figure 8.1.4, involves several irreversible
reactions. Combustion reactions such as the burning of methane are also irreversible:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
Once a fuel has burnt, the products, carbon dioxide and water, do not react with
each other under normal conditions.
As you will see, other reactions are reversible reactions where the products,
once formed, can react again, re-forming the reactants.
You are familiar with the idea that a physical change, such as a state change,
can be reversed. The evaporation of water from lakes and rivers leading to cloud
formation and eventually rain is an example of a physical change. Water can
cycle between the different phases of solid, liquid and gas because each process
is reversible.
In chemistry, a double arrow ( ) is used when writing a chemical equation to
FIGURE 8.1.4 Baking a cake involves a series of show a reversible process. In this way, you can show the phase changes associated
with water using the following equation:
H2O(l) H2O(g)
Many reversible reactions are essential to our society; for example, the reactions
that power rechargeable batteries.
In reversible reactions, the formation of products as a result of collisions between
reactant particles is not the end of the process. Once some products are formed,
collisions between product particles can result in the reactants being re-formed.
Consider the production of ammonia from hydrogen gas and nitrogen gas,
known as the Haber process.
The equation for the reaction can be written as:
N2(g) + 3H2(g) 2NH3(g)
Suppose you mix 1 mol of nitrogen gas and 3 mol of hydrogen gas in a sealed
container. From the equation, you might expect that 2  mol of ammonia would
eventually be formed. However, no matter how long you wait, the reaction seems to
‘stop’ when much less than 2 mol of ammonia is present, as shown in Figure 8.1.5.
volume = 1 L
temperature = 400°C

1.0 mol N2 0.7 mol N2

3.0 mol H2 2.1 mol H2


0.6 mol NH3

initially after a long time


(equilibrium)

FIGURE 8.1.5

196 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
The reaction vessel this process occurs in can be thought of as a closed system
from which the reactants and products cannot escape. Reversible reactions in a
closed system eventually reach a situation where the rate of the forward reaction Reversible reactions can reach
and the rate of the reverse reaction are equal.
At this point, there appears to be no further change to the observer. In the case the overall concentrations of
of a chemical reaction, when the reaction appears to have ‘stopped’, the system
is described as having reached equilibrium. At equilibrium, there still may be
significant amounts of reactants in the system.

CHEMFILE
Limestone caves
An example of reversibility in nature is the formation of stalactites and stalagmites in
limestone caves (Figure 8.1.6).
The main mineral in limestone is calcite (CaCO3). Water saturated with carbon dioxide
from the atmosphere drips through the roof of the cave, resulting in the following
reaction:
CO2(g) + H2O(l) + CaCO3(s) → Ca2+(aq) + 2HCO3–(aq)
As the water seeps through the rocks, it becomes saturated with Ca2+ ions and
HCO3–

Ca2+(aq) + 2HCO3–(aq) → CO2(g) + H2O(l) + CaCO3(s)


3

produce beautiful columns like the ones seen in the Buchan cave system shown in

FIGURE 8.1.6

EXPLAINING REVERSIBILITY
The reason why reversible reactions can occur can be understood by referring to an
energy profile diagram like the ones you saw in section 2.2.
When particles collide, the energy associated with collisions can break bonds in
the reacting particles, allowing them to rearrange to form new products. The energy
required to break the bonds of the reactants is known as the activation energy of
the reaction.
CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 197
You can see from the energy profile diagram shown in Figure 8.1.7 that once the
products form, it is possible for the reverse process to occur. If the newly formed
product particles collide with enough energy to break their bonds (equal to the
activation energy
Energy

activation of reverse reaction


activation energy of the reverse reaction), then it is possible to re-form the original
energy of reactants.
forward
reaction products If the forward reaction is endothermic, the reverse reaction is exothermic, and
ΔH
vice versa.
reactants
Reaction progress EXPLAINING EQUILIBRIUM
FIGURE 8.1.7 Because the reaction between nitrogen and hydrogen to form ammonia is a
reversible reaction, it is best written using an equilibrium arrow:
N2(g) + 3H2(g) 2NH3(g)
Equilibrium arrows indicate that the reaction can occur in both the forward and
reverse directions. These arrows should not be used where the reaction can only
proceed one way.
The idea that processes can be reversed can be used to understand why this
+
N

2
3H reaction reaches equilibrium. When nitrogen gas and hydrogen gas are added to a
2 2NH sealed container at a constant temperature, a sequence of events occurs that can be
3
Rate

H
illustrated by a plot of reaction rate versus time like the one shown in Figure 8.1.8.
+3 2 If you consider the graph in Figure 8.1.8, you can understand the following.
N2
3 • Nitrogen and hydrogen gas molecules collide with each other and form
H
2N

ammonia. As the forward reaction, N2(g) + 3H2(g) → 2NH3(g), proceeds, the


Time concentrations of nitrogen and hydrogen decrease, so the frequency of collisions
between molecules decreases and the rate of the production of ammonia
decreases.
FIGURE 8.1.8
• At the same time as ammonia is being formed, some ammonia molecules collide
forward and reverse reactions with time when
and decompose to re-form nitrogen and hydrogen: 2NH3(g) → N2(g) + 3H2(g).
• Eventually the forward and reverse reactions proceed at the same rate. When
this situation is reached, ammonia is formed at exactly the same rate as it is
breaking down. The concentrations of ammonia, nitrogen and hydrogen then
3 remain constant. To an observer, the reaction now appears to have stopped with
H2
no observable change.
In a closed system at constant pressure and temperature, no further change will
take place. The reaction has reached a point of balance—an equilibrium.
Concentration (M)

2
The concentration versus time graph in Figure 8.1.9 shows the changes in
concentrations of the chemicals with time. Equilibrium is established when there is
no longer any change in any of the concentrations.
1 N2

NH3

Time
N2 and H2
added to DYNAMIC STATE OF EQUILIBRIUM
container Chemical equilibrium can be described as being in a dynamic state because the
FIGURE 8.1.9 Changes in the concentrations forward and reverse reactions have not ceased. Instead, they occur simultaneously
of N2, H2 and NH3 as a mixture of nitrogen at the same rate.
During dynamic equilibrium:
for every mole of N2 that reacts, three times • the reaction is ‘incomplete’ and all of the substances (that is, the reactants and
as much H2 reacts and twice as much NH3 products) are present in the equilibrium mixture
• at the molecular level, bonds are constantly being broken and new bonds are
being formed as the reactants and products continue to be converted from one
to another.

198 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
The decomposition of dinitrogen tetroxide (N2O4) to nitrogen dioxide (NO2)
is an example of a reversible reaction that reaches a dynamic equilibrium. The
progression of this reaction from pure N2O4 to the equilibrium mixture containing by reversible physical or chemical
both N2O4 and NO2 can be monitored through the changing colour of the gases in
the reaction vessel. N2O4 is colourless and NO2 is dark brown.
The reaction occurs according to the following equation:
N2O4(g) 2NO2(g)
Figure 8.1.10 illustrates the observations made of a reaction vessel that is
injected with some pure N2O4. As the forward reaction proceeds, the formation of
a dark brown gas is observed. The depth of colour increases until equilibrium is
reached at which point there is no further change in the colour.

3 seconds 8 seconds 3 hours

N2O4(g) N2O4(g) + NO2(g) N2O4(g) + NO2(g) N2O4(g) + NO2(g)


FIGURE 8.1.10

EXTENSION

Investigating dynamic equilibrium


Chemists can use radioactive isotopes to add radioactive
investigate systems in dynamic equilibrium. sodium iodide
Radioactive isotopes behave chemically in the
same way as non-radioactive atoms of the
same element, but their presence and location
saturated
can be easily determined by a radiation sodium iodide
detector. solution
radiation
When solid sodium iodide (NaI) is added detector
to water, it dissolves readily at first. As the
concentration of dissolved sodium iodide
increases, a saturated solution forms and no solid
further solid dissolves. The concentrations of sodium
iodide
the Na+ ions and I– ions in solution remain
constant and some solid NaI is always present
on the bottom of the test tube.
When solid sodium iodide containing
radioactive iodide ions is added to a saturated
solution, the subsequent movement of these no radiation solution becomes
radioactive
‘labelled’ ions can be traced. Figure 8.1.11
shows that although solid sodium iodide FIGURE 8.1.11

is still observed in the bottom of the flask,


the solution quickly becomes radioactive.

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 199


The radioactivity of the solution shows that some of the radioactive
sodium iodide has dissolved. The concentration of sodium iodide
remains constant, so particles that were not radioactive must have Dissolved
Ions leave
crystallised from the solution at the same rate as the radioactive solid the surface ions return to
was dissolving (Figure 8.1.12). of the solid the surface of
as they the solid at
Even though we see nothing happening, there must be continual dissolve. the same
activity at the surface of the solid. The process is a dynamic rate.
equilibrium:
NaI(s) NaI(aq)
FIGURE 8.1.12
redepositing of ions in a saturated solution

EXTENT OF REACTION
You have seen that reactions are reversible, but do all reactions proceed to the
same extent before they reach equilibrium? This can be answered with a simple
experiment.
Both hydrogen chloride (HCl) and ethanoic acid (CH3COOH) react with water
to form ions, according to the equations:
HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq)
CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO–(aq)
Solutions of both chemicals conduct electricity because they contain mobile
ions. The relative conductivity of the solutions is proportional to the number of
free ions in the solution. By measuring the electrical conductivity of solutions of the
same concentration, you can compare how much each compound ionises in water.
Figure 8.1.13 shows the results obtained from such an experiment. You can
see that the solution formed when hydrogen chloride dissolves in water (called
hydrochloric acid) is a much better conductor than the ethanoic acid solution. Both
solutions were formed by adding the same number of moles of acid molecules to
identical volumes of water.
high conductivity low conductivity
battery A reading A reading

H3O+(aq) H3O+(aq)
Cl−(aq) CH3COO–(aq)
CH3COOH(aq)

1 M HCl(aq) 1 M CH3COOH(aq)

FIGURE 8.1.13

200 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
As you will remember from Unit 2, ethanoic acid is a weak acid and will therefore
only partially ionise in an aqueous solution. Hydrochloric acid is a strong acid that The extent of a reaction does not
almost completely ionises in aqueous solution. The concept of equilibrium allows
us to better explain the idea of strong and weak acids by looking at the extent of the
ionisation reaction.
is formed once the system is
The difference in conductivity observed in the experiment arises because these
reactions occur to remarkably different extents. At equilibrium in a 1 M solution, at
25°C, almost all the HCl molecules are ionised, whereas only approximately 1% of
the CH3COOH molecules are ionised.
We can conclude that different reactions proceed to different extents. The ratios
of reactants to products are different for different equilibrium systems.
It is important to note that the extent of reaction describes how much product
is formed when the system reaches equilibrium. However, the rate of reaction is
a measure of the change in concentration of the reactants and products with time
and is not directly related to the extent of reaction. The rates of reversible reactions
range from very slow to very fast and determine how long the reaction takes to
reach equilibrium.

8.1 Review
SUMMARY

• In a closed system, only energy, not matter, is reverse reaction are equal. At this point, a dynamic
exchanged with the surroundings. equilibrium has been achieved.
• In an open system, both matter and energy • Equilibrium can be achieved in closed systems but
are exchanged between the system and not in open systems.
the surroundings. • Different reactions proceed to different extents.
• A reversible reaction is a reaction in which the • The relative ratios of reactants to products when
products can be converted back to the reactants. equilibrium is reached are different for different
• An irreversible reaction is a reaction in which the reactions.
products cannot be converted back to the reactants. • The extent of reaction indicates how much product
• Reversible reactions can reach a point where the is formed at equilibrium, whereas the rate of
rate of the forward reaction and the rate of the reaction is a measure of the change in concentration
of the reactants and products with time.

KEY QUESTIONS

1 Which one of the following statements about the extent of reaction is true?
A The extent of reaction indicates the rate of the reaction, and indicates
the time taken to reach equilibrium.
B The extent of reaction is the point when there are equal amounts of
reactants and products.
C The extent of reaction indicates how far the reaction has proceeded in
Rate

the forward direction when equilibrium is achieved.


D The extent of reaction indicates the rate of reaction and is the point
when the rate of the forward reaction is equal to the rate of the reverse
reaction.
2 Hydrogen gas is mixed with iodine gas in a sealed container. A reaction
occurs according to the equation:
Time
H2(g) + I2(g) 2HI(g)
On the rate–time graph for this system (Figure 8.1.14), label the lines for FIGURE 8.1.14
the forward and reverse reactions with the appropriate chemical equation.
Also label the point when equilibrium is first established.

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 201


3 Fill in the blanks to complete the sentences about dynamic equilibrium.
In a ____________ system, as the concentrations of the reactants decreases,
the rate of the forward reaction also _______________. The collisions between
these reactant molecules occur ___________ frequently. Once some product
starts to form, the __________ reaction occurs and the frequency of collisions
between product molecules ____________. At equilibrium, the rates of the
forward and backward reactions are ____________ and the concentrations
of all species do not change.
4 The graph in Figure 8.1.15 shows the concentration versus time plot for the
decomposition of dinitrogen tetroxide: N2O4(g) 2NO2(g) at 100°C in a 1 L
reaction vessel. N2O4 is a colourless gas and NO2 is brown. Use the graph to
answer the following questions.

0.10
N2O4(g) 2NO2(g)

NO2
Concentration (M)

0.05

N2O4

2 4 6 8 10 12 14
Time (s)
FIGURE 8.1.15 Graph showing the reaction progress for the reversible decomposition of

a What is the initial concentration of N2O4 in the flask?


b What is the initial concentration of NO2 in the flask?
c What is the concentration of N2O4 at equilibrium?
d What is the concentration of NO2 at equilibrium?
e Over the course of the reaction, how many moles of N2O4 decompose?
f What do the horizontal regions of the graph indicate?
g How long does it take for equilibrium to be reached?
h A student studying this reaction records her observations over time.
What will she observe as the reaction proceeds?

202 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
8.2 The equilibrium law
In this section, you will investigate the relationship between the quantities of
reactants and the quantities of products present when a system reaches equilibrium.
This relationship allows you to qualitatively predict the relative amounts of
reactants and products in individual equilibrium systems.

THE REACTION QUOTIENT


Consider the equilibrium system you were introduced to in section 8.1:
N2(g) + 3H2(g) 2NH3(g)
An unlimited number of different equilibrium mixtures of the three gases,
nitrogen, hydrogen and ammonia, can be prepared. Table 8.2.1 shows the
concentrations of each of these gases in four different equilibrium mixtures at
[NH3]2
a constant temperature of 400°C. The values of the fraction for each
[N2][H2]3
mixture are also given.
[NH3]2
The fraction is called the reaction quotient (Qc) or concentration
[N2][H2]3
fraction of the mixture.

TABLE 8.2.1 Concentrations of reactants and products present in equilibrium mixtures

Equilibrium [N2] (M) [H2] (M) [NH3] (M) [NH3]2


mixture [N2][H2]3

1 0.25 0.75 0.074 0.052

2 0.25 0.65 0.089 0.052

3 0.0025 0.0055 4.6 × 10–6 0.051

4 0.0011 0.0011 2.7 × 10–7 0.051

[NH3]2
As you can see in Table 8.2.1, the reaction quotient [N ][H ]3 has an almost
2 2
constant value of 0.052 for each equilibrium mixture regardless of the concentration
of each component. Note that the coefficients of the reactants and products in the
chemical equation above form the indices of the respective reactant and product
concentrations used in the reaction quotient.
While the reaction quotient can be calculated for any mixture of reactants and
products at any time during a reaction, it is only when the mixture is at equilibrium
that it gives a constant value. At equilibrium, the value of the reaction quotient is
equal to the equilibrium constant, Kc.
In general, for chemical reactions at equilibrium:
• different chemical reactions have different values of Kc
• the size of Kc indicates the proportions (relative amounts) of reactants and
products in the equilibrium mixture
• for a particular reaction, Kc is constant for all equilibrium mixtures at a fixed
temperature.

Kc Kc is different for

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 203


THE EXPRESSION FOR THE EQUILIBRIUM LAW
By studying a large number of reversible systems such as the one between nitrogen,
hydrogen and ammonia in the previous example, chemists have been able to
develop the concept of the equilibrium law.
The equilibrium law states that the:
• equilibrium constant, Kc, is the concentrations of products divided by the
concentrations of reactants at equilibrium
• index of each component concentration is the same as the coefficient for the
substances in the balanced chemical equation.
For the general equation aW + bX cY + dZ at equilibrium at a particular
temperature, the equilibrium expression can be written as:
[Y]c[Z]d
Kc =
[W]a[X]b
where Kc is the equilibrium constant.
A useful way of remembering the equilibrium law is that:
[products]coefficients
Kc can be represented as . Remember that if there is more than
[reactants]coefficients
expression, the concentrations of one product or reactant, you must multiply the terms.

Units for equilibrium constants


Units for equilibrium constants depend on the expression used to represent the
chemical reaction. They can be determined by substituting M or mol L–1, for
each concentration into the concentration fraction expression. In the case of the
equilibrium between nitrogen, hydrogen and ammonia above, since:
[NH3]2
Kc =
[N2][H2]3
Kc depend on the the unit is given by:
M2
= M–2 (or mol–2 L2)
M × M3

Worked example 8.2.1


DETERMINING THE UNITS FOR AN EQUILIBRIUM EXPRESSION

The decomposition of N2O4 is a reversible reaction that occurs according to


the equation:
N2O4(g) 2NO2(g)
Write the expression for the equilibrium constant Kc and determine its units.

Thinking Working

Write the expression for Kc. [NO2]2


Kc =
[products]coefficients [N2O4]
[reactants]coefficients
Substitute the units of concentration M2
= M = mol L–1
into the expression for Kc . M
Solve to find the units of Kc.

204 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
DETERMINING THE UNITS FOR AN EQUILIBRIUM EXPRESSION

Write the equilibrium expression and determine the units for Kc for the
reversible reaction:
2SO2(g) + O2(g) 2SO3(g)

An expression for the equilibrium constant, Kc, can be written for any system at
equilibrium. As you learned earlier, a similar expression can be written, called a
reaction quotient, Qc (or concentration fraction), for systems that are not necessarily
at equilibrium. For:
aA + bB cC + dD
[C]c[D]d
Qc =
[A]a[B]b
A reaction quotient can be calculated for any mixture of reactants and products
at any time during a reaction. However, it is only when the mixture is at equilibrium
that the reaction quotient is a constant value. At equilibrium, the value of the
reaction quotient is equal to the equilibrium constant, Kc.
If the reaction quotient is:
• greater than Kc, the system ‘shifts to the left’ to achieve equilibrium and more
reactants are formed
• smaller than Kc, the system ‘shifts to the right’ to achieve equilibrium and more
products are formed
• equal to Kc, the system is at equilibrium.
The relationship between Qc and Kc is illustrated in Figure 8.2.1. By comparing
the value of Qc for a reaction to Kc at a given temperature, it is possible to predict
the direction a reaction will proceed in order to reach equilibrium.

equilibrium

Qc

[products] [products]
Kc Kc
Qc Kc
[reactants] [reactants]

Qc The reaction shifts to the right The reaction shifts to the left
toward the products to toward the reactants to
increase Qc and reach decrease Qc and reach
eqilibrium. eqilibrium.

Qc < Kc Qc = Kc Qc > Kc

FIGURE 8.2.1 For any reversible reaction at equilibrium Kc = Qc , so comparing these two values for

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 205


CHEMFILE
Equilibrium in the theatre
A yellow solution containing Fe3+ ions reacts with a colourless
solution containing SCN– ions to form a blood-red coloured solution
containing FeSCN2+ ions, according to the equilibrium reaction:
Fe3+(aq) + SCN–(aq) FeSCN2+(aq) Kc = 9 × 102 –1 at 25°C
An appreciable amount of the product FeSCN2+ is present

This equilibrium reaction is used in theatrical productions to make


fake blood. A layer of colourless SCN– solution can be painted
onto an actor’s hand prior to the scene. If a plastic knife that has
been previously dipped in pale yellow Fe3+ solution is used to make FIGURE 8.2.2
right: a solution containing Fe3+, a solution containing SCN–, and an
a fake cut across the hand, a blood-red ‘cut’ appears due to the
equilibrium mixture of Fe3+, SCN– and FeSCN2+
production of red FeSCN2+.

Homogeneous and heterogeneous equilibria


The chemical reactions discussed so far have involved homogeneous reactions,
in which all reactants and products are in the same state or phase. Homogeneous
equilibria are the focus of this chemistry course. However, some equilibria involve
heterogeneous reactions, in which reactants and products are in different states
or phases. The following extension section describes how to write an equilibrium
law for a heterogeneous equilibrium.

EXTENSION

Equilibria in heterogeneous reactions


The important feature of the equilibrium law for heterogeneous reactions
is that the concentration of a pure solid or a pure liquid is assigned as 1.
This is because these concentrations do not depend on how much of the
pure substance is present.
Because the concentration of the solid in the heterogeneous system
is considered a constant, it is removed from the equilibrium expression.
As a result, the expression for the equilibrium of a heterogeneous system
is often much simpler.
For example, for the equation:
CaCO3(s) CaO(s) + CO2(g)
the expression for the equilibrium constant is Kc = [CO2]. CaO and CaCO3 are
both solids and do not appear in the equilibrium law.
The dissolution of a solid into an aqueous solution is another example of
a heterogeneous equilibrium system.
Consider the dissociation of lead chloride (PbCl2) into lead and chloride ions
in solution:
PbCl2(s) Pb2+(aq) + 2Cl–(aq)
Because the concentration of the lead chloride is constant, it can be said to
be equal to 1 and simply removed from the expression for the equilibrium law.
This results in the expression:
Kc = [Pb2+][Cl–]2

206 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
8.2 Review
SUMMARY

• The equilibrium constant, Kc, is a constant for The reaction quotient, Qc, has the same
a particular chemical reaction at a particular mathematical expression as the equilibrium law.
temperature. • When a reaction system at a particular temperature
• The equilibrium law for the equation: has reached equilibrium, the reaction quotient is
aW + bX cY + dZ equal to the equilibrium constant.
is: • The unit for an equilibrium constant depends on
[Y]c[Z]d the equation for the equilibrium. The unit can be
Kc =
[W]a[X]b determined by substituting M (mol L–1), for each
• A reaction quotient (concentration fraction) can concentration into the reaction quotient.
be calculated for any stage of a chemical reaction.

KEY QUESTIONS

1 Write an expression for the reaction quotient for the reaction of hydrogen
and chlorine with the equation:
H2(g) + Cl2(g) 2HCl(g)
2 At a particular temperature, the equilibrium constant for the reaction
represented by the following equation is 0.667 M–2:
CO(g) + 3H2(g) CH4(g) + H2O(g)
At a specific point in the reaction, the reaction quotient is found to be
0.234 M–2. With reference to the concentration of the products, predict
which way the reaction will shift in order to reach equilibrium.
3 Define:
a homogenous system
b reaction quotient
c equilibrium constant.
4 Consider the reaction represented by the equation:
Cu2+(aq) + 4NH3(aq) [Cu(NH3)4]2+(aq)
At 25°C the equilibrium constant is determined to be Kc = 0.46 M–4.
At a particular time during the reaction, the reaction quotient is 1.2 M–4.
Write an expression for the reaction quotient for this reaction and predict
what will happen to the system as it moves to equilibrium.

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 207


8.3 Working with equilibrium
constants
In section 8.2, you learned that an equilibrium law can be written for a chemical
reaction at equilibrium. The mathematical expression for the equilibrium law is a
fraction involving the concentrations of the reactants and products, which has a
value equal to Kc, the equilibrium constant for the reaction at equilibrium.
The value of an equilibrium constant indicates the extent of a reaction or how
far a reaction will proceed towards the products. In this section, you will learn how
to interpret these values in terms of the relative amounts of reactants and products
present at equilibrium.
You will also discover how temperature affects an equilibrium constant and
what happens to the value of an equilibrium constant when an equation is reversed
or the coefficients of the equation are changed.

DEPENDENCY OF AN EQUILIBRIUM CONSTANT


ON THE EQUATION
The equilibrium law depends upon the chemical equation used for a particular
reaction.
For example, the equilibrium between the gases N2O4 and NO2 can be
represented by several equations. For each equation provided below, the expression
for the equilibrium constant, Kc, is also given.
[NO2]2
N2O4(g) 2NO2(g) Kc =
[N2O4]
[N2O4]
2NO2(g) N2O4(g) Kc =
[NO2]2
[NO2]4
2N2O4(g) 4NO2(g) Kc =
[N2O4]2
1 [NO2]
N2O4(g) NO2(g) Kc = 1
2 [N2O4]2
You can see from these expressions that if:
• one equation is the reverse of another, the equilibrium constants are the inverse
(or reciprocal) of each other
Kc, • the coefficients of an equation are doubled, the value of Kc is squared
• the coefficients of an equation are halved, the value of Kc is the square root of
the original value of Kc.
Therefore, it is important to specify the equation when quoting an equilibrium
constant.

THE MEANING OF THE VALUE OF AN EQUILIBRIUM


CONSTANT
The value of an equilibrium constant is based on the equilibrium concentrations of
the products divided by the equilibrium concentrations of the reactants. Therefore,
it indicates the extent of reaction at equilibrium (how far the forward reaction
proceeds before equilibrium is established) and the equilibrium yield (the
amount of products present at equilibrium).

Kc

208 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
The relationship between the value of Kc and the relative proportions of
reactants and products at equilibrium is shown in Table 8.3.1.

TABLE 8.3.1 Kc and the extent of a reaction provides

Value of Kc Extent of reaction

Between about The extent of reaction is significant. Appreciable concentrations


10–4 and 104 of both reactants and products are present at equilibrium.
e.g. N2(g) + 3H2(g) 2NH3(g) Kc = 0.52 M–2 at 400°C

Very large; >104 Almost complete reaction occurs. The concentrations of products are
much higher than the concentrations of the reactants at equilibrium.
e.g. HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq) Kc = 107 M at 25°C

Very small; <10–4 Negligible reaction occurs. The concentrations of reactants


are considerably higher than the concentrations of products
at equilibrium.
e.g. CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO–(aq)
Kc = 1.8 × 10–5 M at 25°C

When Kc is very large, the numerator of the equilibrium expression must


be large compared to the denominator, which means there is a large amount of
products relative to the amount of reactants.
When Kc is very small, the numerator of the equilibrium expression must be very
small compared to the denominator, which means there must be a large amount of
reactants relative to the amount of products.

Effect of temperature on an equilibrium constant


It has been shown experimentally that the value of the equilibrium constant, Kc,
for a particular reaction depends only upon temperature. It is not affected by the
addition of reactants or products, changes in pressure, or the use of catalysts.
The effect of a change in temperature on an equilibrium constant depends on
whether the reaction is exothermic or endothermic. As temperature increases, for:
• exothermic reactions, the value of Kc decreases and so the amount of products
present at equilibrium decreases
• endothermic reactions, the value of Kc increases and so the amount of products
present at equilibrium increases.

Kc

Table 8.3.2 summarises the effect on Kc when temperature increases. The


opposite is true when temperature decreases.

TABLE 8.3.2 Kc when the temperature of the system increases

∆H T Kc

Exothermic (–) Increases Decreases

Endothermic (+) Increases Increases

Because the value of Kc depends on temperature, it is essential to specify the


temperature at which an equilibrium constant has been measured.

CHAPTER 8 | EXTENT OF CHEMICAL REACTIONS 209


8.3 Review
SUMMARY

• The equilibrium constant, Kc, is specific for • When an equation is reversed, the new equilibrium
an equation. constant is the reciprocal, or inverse, of the
• The value of Kc provides a measure of the extent of original Kc.
reaction and the relative concentrations of reactants • When coefficients are doubled, Kc is squared.
and products at equilibrium. • As temperature increases, the value of Kc increases
for endothermic reactions and decreases for
Value of Kc Extent of reaction
exothermic reactions.
Between about Indicates significant reaction occurs
10–4 and 104

>104 Indicates an almost complete reaction


occurs

<10–4 Indicates negligible reaction occurs

KEY QUESTIONS

1 The equilibrium constant for the decomposition of 3 For the chemical reaction: PCl5(g) PCl3(g) + Cl2(g)
ammonia is 100 M2 at 255°C for the equation: the equilibrium constant is 1.70 M at 250°C.
2NH3(g) N2(g) + 3H2(g) For each equation, calculate the value of Kc at the
a Write an expression for the equilibrium constant for same temperature.
the equation: a 4PCl5(g) 4PCl3(g) + 4Cl2(g)
N2(g) + 3H2(g) 2NH3(g) 1 1 1
b PCl3(g) + Cl2(g) PCl5(g)
b Calculate the equilibrium constant for the equation 2 2 2
given in part a. 1 1 1
c PCl5(g) PCl3(g) + Cl2(g)
2 2 2
c Write an expression for the equilibrium constant for
d 2PCl3(g) + 2Cl2(g) 2PCl5(g)
the equation:
1 3 4 A chemist investigated three different reactions and
NH3(g) N (g) + H2(g)
2 2 2 determined the value of the equilibrium constant
d Calculate the equilibrium constant for the equation for each. In which of the reactions would there be
in part c. substantially more products produced compared
e Use your answers to parts a–d to state the effect on to reactants?
the value of an equilibrium constant when the: A Reaction 1: Kc = 0.0057
i equation is reversed B Reaction 2: Kc = 2.5 × 109
ii coefficients of the equation are halved. C Reaction 3: Kc = 3.1 × 10–3
2 Water reacts with chlorine according to the equation: 5 State whether the equilibrium constants for each
2H2O(g) + 2Cl2(g) 4HCl(g) + O2(g) of the following would be increased, decreased or
At a particular temperature the value of the unchanged by an increase in temperature:
equilibrium constant for this reaction is determined to a 2NH3(g) N2(g) + 3H2(g) ∆H = +91 kJ mol–1
be 4.0 × 10–4 M. Assuming no change in temperature, b 4HCl(g) + O2(g) 2H2O(g) + 2Cl2(g)
calculate the value for the equilibrium constant for ∆H = –113 kJ mol–1
the reaction: c H2(g) + CO2(g) H2O(g) + CO(g)
1
a H2O(g) + Cl2(g) 2HCl(g) + O2(g) ∆H = +42 kJ mol–1
2
1 d 2CO(g) + O2(g) 2CO2(g) ∆H = –564 kJ mol–1
b 2HCl(g) + O2(g) H2O(g) + Cl2(g)
2

210 AREA OF STUDY 2 | HOW CAN THE YIELD OF A CHEMICAL PRODUCT BE OPTIMISED?
8.4 Calculations involving equilibrium
In section 8.3, you saw that for a reversible reaction, an expression for an
equilibrium constant, Kc, can be written as a ratio of the molar concentrations of
the products to the molar concentrations of the reactants. In this section, you will
learn to determine equilibrium constants given molar concentrations. You will also
learn to calculate the concentration of a reactant or product using the equilibrium
constant at a specified temperature.
Although the calculations in this section will be restricted to chemical equilibria,
the same principles can be applied to other systems in our surroundings. For
example, on the African plains of Tanzania, there is a delicate balance of herbivores
such as zebras and wildebeest, and carnivores such as lions (Figure 8.4.1). If the
populations change through drought or disease, the relative numbers change and FIGURE 8.4.1
a new balance is established. This new balance can be predicted in much the same lions in Africa can be understood using the
way as occurs for chemical equilibrium.

CALCULATIONS INVOLVING THE EQUILIBRIUM CONSTANT


AND CONCENTRATIONS
Calculating an equilibrium constant
An equilibrium constant can be calculated from the molar concentrations of
reactants and products at equilibrium, as shown in Wo